EP2408305A1 - Pyrimindine-4-ylpropane dinitrile derivatives, method for the production thereof, and use thereof as herbicide and plant growth regulators - Google Patents

Pyrimindine-4-ylpropane dinitrile derivatives, method for the production thereof, and use thereof as herbicide and plant growth regulators

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Publication number
EP2408305A1
EP2408305A1 EP10709800A EP10709800A EP2408305A1 EP 2408305 A1 EP2408305 A1 EP 2408305A1 EP 10709800 A EP10709800 A EP 10709800A EP 10709800 A EP10709800 A EP 10709800A EP 2408305 A1 EP2408305 A1 EP 2408305A1
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EP
European Patent Office
Prior art keywords
alkyl
radicals
alkoxy
haloalkyl
optionally substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10709800A
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German (de)
French (fr)
Inventor
Hansjörg Dietrich
Hartmut Ahrens
Michael Gerhard Hoffmann
Jan Dittgen
Dieter Feucht
Christopher Hugh Rosinger
Isolde HÄUSER-HAHN
Marco BRÜNJES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
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Bayer CropScience AG
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Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP10709800A priority Critical patent/EP2408305A1/en
Publication of EP2408305A1 publication Critical patent/EP2408305A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom

Definitions

  • the present invention relates to novel, herbicidally active pyrimidin-4-ylpropandinitrile derivatives and to processes for their preparation.
  • Another object of the present invention is its use as a herbicide, in particular as a herbicide for the selective control of harmful plants in crops, and as a plant growth regulator alone or in combination with safeners and / or in admixture with other herbicides.
  • EP 0 136 976 A discloses 2-phenyl-substituted pyrimidines which are known as
  • Growth regulators are used. However, a herbicidal action is not disclosed, any more than the substitution pattern according to the invention.
  • DE 25 20 381 A1 likewise discloses pyrimidine-based plant growth regulators, which however only carry aliphatic hydrocarbon substituents on pyrimidine.
  • R 1 is phenyl, optionally substituted by 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 4 ) hydroxyalkyl, (C 2 - C 4 ) alkoxyalkyl, (C 2 -C 4 ) haloalkoxyalkyl,
  • (C 1 -C 6 ) -alkyl optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) -haloalkenyl, (C 1 -C 3 ) -alkoxy, (Cr C 2 ) haloalkoxy, (dC 3 ) alkylthio, (CrC 2 ) haloalkylthio or optionally substituted aryl; or
  • (C 2 -C ⁇ ) alkenyl optionally substituted by 1-3 radicals R z, which are independently halo, (C r C6) alkyl, (CrC 6) haloalkyl, (C 1 -C 3) -alkoxy, (G 1 - C 2 ) haloalkoxy, (C r C 3 ) alkylthio or (C r C 2 ) haloalkylthio;
  • R 2 is H, F, Cl, Br, I, CN, NO 2 , OR 5 , SR 6 or N (R 7 ) R 8 ; wherein R 5 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl, R 6 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl and R 7 and R 8 are independently H or (C 1 -C 4 ) alkyl;
  • N C (R 17 ) R 18 ;
  • each radical R 9 , R 10 and R 11 is independently halogen, (Cr
  • R 12 is each independently H, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (Cr
  • R 13 is H, (C r C 4 ) alkyl, (CrC 3 ) haloalkyl or CHR 25 C (O) OR 26 ;
  • R 14 is (C r C 4 ) alkyl or (Ci-C 3 ) haloalkyl;
  • R 16 is H or (C r C 4 ) alkyl;
  • R 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals independently of one another representing CH 3 , Cl or OCH 3 ;
  • R 18 is H or (Ci-C 4) alkyl; or R 17 and R 18 together form a group
  • R 19 is in each case independently halogen, (C 1 -C 3 ) -alkyl, (C 1 -C 3 ) -alkoxy,
  • R 20 is H or (C 1 -C 4 ) alkyl
  • R 21 and R 22 are independently H or (C 1 -C 4 ) alkyl
  • R 23 is H or (C r C 4 ) alkyl;
  • R 24 is (C r C 4 ) alkyl;
  • R 25 is H, (Ci-C 4 ) alkyl, (C r C 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or
  • R 26 is H, (C r C 4 ) alkyl or (C r C 4 ) alkoxy;
  • R 27 is H, (C 1 -C 4 ) alkyl or benzyl;
  • R 28 is each independently halogen, cyano, nitro, (C 1 -C 6 alkyl, (Cr
  • a dimethylaminocarbonyl radical is a C 3 -ReSt.
  • R 1 is phenyl, optionally substituted by 1-3 R x radicals, which independently represent halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 4) alkoxyalkyl, (C 2 -C 4) haloalkoxyalkyl, (C 2 -C 4) alkenyl, (C 2 - C 4) haloalkenyl, (C 2 -C 4) alkynyl, (C 3 -C 4) haloalkynyl, hydroxy , (C 1 -C 4) -alkoxy, (C 1 - C 4) haloalkoxy, (CrC 4) alkylthio, (C r C4) haloalkylthio, (C r C4) alkylsul
  • (C 1 -C 6 ) alkyl optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy, (C r C 2 ) haloalkylthio or optionally substituted phenyl; or
  • (C 2 -C 6 ) alkenyl optionally substituted by 1-3 radicals R z , which independently of one another are halogen, (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -haloalkyl, (C 1 -C 3 ) -alkoxy, (C 1 -C 2 ) haloalkoxy, (C r C 3 ) alkylthio or (C r C 2 ) haloalkylthio;
  • R 2 is H, F, Cl, Br, I, CN or NO 2 ;
  • R 3 and R 4 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 O (CH 2 ) 2 - or
  • each R 9, R 10 and R 11 are each independently halogen, (C 1 - C 3) alkoxy, (C 1 -C 3) HaIOaIkOXy, (C r C 3) alkylthio, (CrC 3) haloalkylthio, amino,
  • R 12 is independently H, (CrC 4) alkyl, (CrC 3) haloalkyl, (C 1 - C 4 ) alkoxy, phenyl, phenoxy or benzyloxy;
  • R 13 is H, (C 1 -C 4 ) alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O) OR 26 ;
  • R 16 is H or (C r C 4 ) alkyl;
  • R 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals independently of one another representing CH 3 , Cl or OCH 3 ;
  • R 18 is H or (C 1 -C 4 ) alkyl; or R 17
  • R 20 is H or (C r C 4 ) alkyl
  • R 21 and R 22 are independently H or (Ci-C 4 ) alkyl
  • R 25 is H, (dC 4 ) alkyl, (CrC 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or
  • R 26 is H, (dC 4) alkyl or (C r C 4) alkoxy.
  • R 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently represent halogen, carboxyl, cyano, nitro, (Ci-C ⁇ ) alkyl, (Cr
  • R 2 is F, Cl, Br, I or NO 2 ;
  • R 4 is H or (C r C 4 ) alkyl
  • R 3 and R 4 together form a group - (CH 2 ) 2 O (CH 2 ) 2 -.
  • R 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) haloalkyl, (C 1 -C 4 ) alkoxy, (C r C 4 ) haloalkoxy; or (C 1 -C 6 ) alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy or unsubstituted or substituted by a halogen; or (C 2 -C 6) alkenyl optionally substituted by 1-3 radicals R z, which independently of one another, halogen (C 1 -C 6) -alkyl, (CrC 6) haloalkyl, (C 1 -C 3) -alkoxy or (CrC 2 )
  • R 1 is phenyl, optionally substituted with 1-3 R x radicals, which independently represent halogen, carboxyl, nitro, (C 1 -C 6 alkyl, (C 1 -C 6 haloalkyl, (C 1 -C 4 ) alkoxy;
  • (C 1 -C 6 ) alkyl optionally substituted with 1-3 radicals R y , which independently represent halogen, phenyl or 4-halo-phenyl;
  • R 2 is F, Cl, Br or NO 2 ;
  • R 3 is H or (C r C 4 ) alkyl
  • R 4 is H or (C r C 4 ) alkyl.
  • the compounds of the formula (I) can form tautomers by hydrogen displacement, which are also the subject of the present invention.
  • the pyrimidin-4-ylpropandinitrile derivatives (I) can also be present as pyrimidine-4 (3 / - /) - ylidene-divinitriles (Ia) or as pyrimidine-4 (7 / - /) - ylidene-divinitriles (Ib), according to the invention all tautomers are included, in particular the forms (I), (Ia) and (Ib).
  • the compounds of formula (I) may, depending on the nature and linkage of
  • Stereoisomers exist as stereoisomers.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, geometric isomers and atropisomers, and mixtures thereof are all encompassed by formula (I).
  • diastereomers can occur.
  • asymmetric carbon atoms asymmetrically substituted carbon atoms
  • sulfur atoms in the form of sulfoxides, which may exist in two enantiomeric forms, enantiomers and
  • Stereoisomers occur.
  • Stereoisomers can be prepared from the mixtures obtained in the preparation by conventional separation methods, for example by chromatographic separation process, isolate.
  • stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants.
  • the invention thus also relates to all stereoisomers which are encompassed by the general formula (I), even if they are not specified with their specific stereoform, and mixtures thereof.
  • the compounds of the formula (I) can form agrochemically suitable salts.
  • Salt formation can in a known manner, for. Example, by the action of a base on such compounds of formula (I), which carry an acidic hydrogen atom, for example, in the case that R 1 contains an OH group or a sulfonamide group -NHSO 2 -.
  • Salt formation can also be achieved by the action of a base on CH-acidic compounds, such as (substituted) propanedinitriles.
  • Suitable bases are, for example, organic amines, such as trialkylamines, morpholine, piperidine or pyridine, and ammonia, ammonium, alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and potassium bicarbonate.
  • organic amines such as trialkylamines, morpholine, piperidine or pyridine
  • ammonia ammonium, alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and potassium bicarbonate.
  • salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also salts with organic amines or ammonium salts, for example with ammonium ions of the formula NRR 'R “R”'] ⁇ wherein R, R ', R “and R'” are each independently H or an organic radical, in particular (C- ⁇ -C6) alkyl, (C 6 -C 0) aryl, (C 7 -C 2 o) aralkyl or (C 7 -C 2 o) alkylaryl represent.
  • an agriculturally suitable cation for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also salts with organic amines or ammonium salts, for example with ammonium ions of the formula NRR 'R “R”'] ⁇ wherein R
  • Examples are [NH 4 J + , [NH 3 CH 3 J + , [NH 2 (CH 3 ) Z] + , [NH (CH 3 ) 3 ] ⁇ [N (CH 3 M + , [NH 2 CH 3 C 2 Hs] + or [NH 2 CH 3 CeH 5 ] + .
  • alkylsulfonium and alkylsulfoxonium salts such as (CrCO-trialkylsulfonium and (C 1 -C 4 ) -trialkylsulfoxonium salts.
  • the compounds of formula (I) may be prepared by addition of a suitable inorganic or organic acid, for example mineral acids such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, e.g. As carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid, or sulfonic acids, such as p-toluenesulfonic acid, to a basic group such as amino, alkylamino, dialkylamino, piperidino, Mo ⁇ holino or pyridino, salts. These salts then contain the conjugate base of the acid as an anion.
  • mineral acids such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3
  • organic acids e.g.
  • carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicy
  • Suitable substituents which are present in deprotonated form such as, for example, sulfonic acids, carboxylic acids or CH-acidic groups, such as propanedinitriles, can also form internal salts with groups which can themselves be protonated, such as amino groups.
  • the compounds of formula (I) may form N-oxides.
  • the N-oxides may be known in z. B. by oxidation of the respective pyrimidines with peroxycarboxylic acids or hydrogen peroxide in solvents such as acetonitrile, dichloromethane, chloroform, acetone, DMF, acetic acid, eg. B. at temperatures between 0 ° and 100 0 C are formed (see: S. von Angerer, Science of Synthesis 2003, 16, 548-550 and each cited therein literature).
  • An inorganic radical is a radical without carbon atoms, preferably halogen, OH and its inorganic salts in which the H is replaced by a cation, for example alkali metal and alkaline earth metal salts, -NH 2 and its ammonium salts with (inorganic) acids, for example mineral acids, N 3 (azide), -N 2 + A " (diazonium group, wherein A " represents an anion), -NO, -NHOH, -NHNH 2 , -NO 2 , -ONO, -ONO 2 , -SH, - SOH (sulfenic acid group), -S (O) OH (sulfinic acid group), -S (O) 2 OH (or also short SO 3 H, sulfonic acid group), -O-SO 2 H (sulfite group) , -O-SO 3 H (sulfate group), -SO 2 NH 2 (sulfamoyl group), -
  • organic radical also includes the hydrogen radical (the hydrogen atom), which in the definitions often already part of the unsubstituted body of an organic radical is (example "unsubstituted phenyl”);
  • organic radical here preferably does not include pseudohalogen groups such as CN, SCN, organic metal complexes, carbonate or COOH, which are assigned to the organic radicals because of the content of carbon atoms.
  • Alkyl is straight-chain, branched or cyclic
  • (C 1 -C 4 ) alkyl denotes, for example, a short notation for alkyl having one to 4 carbon atoms corresponding to the range given for C atoms and includes, for example, the radicals methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, cyclopropyl and cyclobutyl.
  • General alkyl radicals having a larger specified range of carbon atoms eg.
  • straight-chain, branched or cyclic alkyl radicals with a larger number of carbon atoms ie, according to the example, also the alkyl radicals having 5 and 6 carbon atoms, are also included in the hydrocarbon radicals such as alkyl, for example "(C 1 -C 6) alkyl" -, alkenyl and alkynyl, even in assembled radicals, the lower
  • Alkyl radicals including in the assembled radicals such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, cyclo, n- or i-propyl, cyclo, n-, i-, t- or 2-butyl, pentyls, hexyls, such as cyclohexyl, n-hexyl, i-hexyl and 1, 3-dimethylbutyl, heptyls such as cycloheptyl, n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl.
  • Preferred cyclic alkyl radicals preferably have 3-8 ring C atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cyclic systems are included with substituents, wherein substituents having a double bond on the cyclic alkyl radical, for.
  • an alkylidene group such as methylidene, are included.
  • polycyclic aliphatic systems are also included, such as bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentan-1-yl , Bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, bicyclo [2.2.1] hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2 yl.
  • spirocyclic aliphatic systems are also included, such as spiro [2.2] pent-1-yl, spiro [2.3] hex-1-yl, spiro [2.3] hex-4-yl, 3-spiro [ 2.3] hex-5-yl.
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated straight-chain, branched or cyclic radicals corresponding to the alkyl radicals, wherein at least one double bond or triple bond is contained. Preference is given to radicals having a double bond or having a triple bond.
  • Alkenyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one double bond, such as 1, 3-butadienyl, 1, 4-pentadienyl or cyclohexadienyl, but also allenyl or cumulylene radicals having one or more cumulative double bonds, such as allenyl (1,2-propadienyl), 1,2-butadienyl and 1,2,3-pentatrienyl.
  • Alkynyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one triple bond or else having one or more triple bonds and one or more double bonds, for example 1,3-butatrienyl or 3-penten-1-yn-1-yl.
  • Alkenyl means e.g. Vinyl, which may optionally be substituted by further alkyl radicals, e.g. Prop-1-en-1-yl, but-1-en-1-yl; Allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl,
  • (C 2 -C 6 ) -alkynyl is, for example, ethinyl, propargyl, 1-methyl-prop-2-yn-1-yl, 2-butynyl, 2-pentynyl or 2-hexynyl, preferably propargyl, but-2-yn 1-yl, but-3-yn-1-yl or 1-methyl-but-3-yn-1-yl.
  • Cyclic alkenyl radicals represent a carbocyclic, non-aromatic, partially unsaturated ring system preferably having 4-8 C atoms, e.g. 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1, 3-cyclohexadienyl or 1, 4-cyclohexadienyl, wherein also substituents with a Double bond on Cycloalkenylrest, z.
  • an alkylidene group such as methylidene, are included.
  • the explanations for substituted cyclic alkyl radicals apply correspondingly.
  • Alkylidene e.g. B. also in the form (CrCi O ) alkylidene, means the radical of a straight-chain, branched or cyclic hydrocarbon radical, which is bonded via a double bond.
  • Aryl is a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
  • aryl In the case of optionally substituted aryl, more cyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, are included, the binding site being on the aromatic system.
  • aryl is also encompassed by the term "optionally substituted phenyl”.
  • substituted by one or more radicals are, if not is defined differently, independently of one another, meaning one or more identical or different radicals, it being possible for two or more radicals to form one or more rings on one cycle as the main body.
  • Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 radicals selected from the group consisting of halogen, alkoxy, alkylthio, hydroxy, amino, nitro, carboxy or a carboxy group equivalent group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as Acylamino, mono- and dialkylamino, trialkylsilyl and optionally substituted cyclic alkyl, optionally substituted aryl, optionally substituted heterocyclyl, wherein each of the latter cyclic groups may also be
  • substituents in addition to the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, Alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and
  • substituted cyclic radicals having aliphatic moieties in the ring cyclic systems are also included having such substituents attached to the ring by a double bond, e.g. B. substituted with an alkylidene group such as methylidene or ethylidene or an oxo group, imino group or substituted imino group.
  • radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and optionally further substituted.
  • the fused rings are preferably 5- or 6-membered rings, particularly preferred are benzo-fused rings.
  • first substituent level if they contain hydrocarbon-containing moieties, may optionally be further substituted there (“second substituent plane"), for example by one of the substituents as defined for the first substituent level.
  • second substituent plane corresponds further substituent levels.
  • substituted radical includes only one or two substituent levels.
  • Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF 5 , aminosulfonyl, alkyl, alkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkanoyl- amino, alkoxy, alkenyloxy, alkynyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, alkenylthio, alkynylthio,
  • Substituents composed of plural substituent levels are preferably, for example, alkoxyalkyl such as monoalkoxyalkyl or dialkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy such as monoalkoxyalkoxy or
  • substituents are selected from the group halogen, for example fluorine and chlorine, (Ci-C 4) alkyl, preferably methyl or ethyl, (Ci-C4) haloalkyl, preferably trifluoromethyl, (CrC 4) -alkoxy, preferably methoxy or ethoxy , (CrC 4 ) haloalkoxy, nitro and cyano.
  • halogen for example fluorine and chlorine
  • substituents methyl, methoxy, fluorine and chlorine.
  • Substituted amino such as mono- or disubstituted amino means a radical from the group of substituted amino radicals which are N-substituted, for example by one or two identical or different radicals from the group alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably mono- and dialkyl-amino, mono- and diarylamino, such as optionally substituted aniline, acylamino, N 1 N- diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; while alkyl radicals having 1 to 4 carbon atoms are preferred;
  • Aryl is preferably phenyl or substituted phenyl; for acyl, the definition below applies, preferably (dC 4 ) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
  • Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.
  • a group equivalent to carboxy group means an alkyl ester, aryl ester, O-alkyl thioester, S-alkyl dithioester, S-alkyl thioester, carboximide ester, carboximide thioester; 5,6-dihydro-1,2,4-dioxazin-3-yl; 5,6-dihydro-1,2,4-oxathiazin-3-yl, trialkylorthoesters, dialkoxyalkylaminoesters, dialkylaminoalkoxyesters, trialkylaminoesters, amidines, dialkoxyketene acetals or dialkyldithioketene acetals.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times by the same or different radicals from the group halogen, (C- ⁇ -C 4) alkyl, (CrC 4) alkoxy, (Ci -C 4) AIkOXy- (C 1 -C 4) alkoxy, (CrC 4) alkoxy (C 1 - C4) alkyl, (C r C 4) haloalkyl, (CrC 4) haloalkoxy, (CrC 4) alkylthio, (CrC 4) haloalkylthio, cyano, isocyano and nitro, for example o-, m- and p-tolyl, Dimethylphenyle , 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and -Trichlormethyl
  • Optionally substituted heterocyclyl is preferably heterocyclyl is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group halogen, cyano, (C r C4) alkyl, (CrC 4) -alkoxy, (CrC 4) alkoxy - (C r C 4) alkoxy, (CrC 4) alkoxy (Ci-C 4) alkyl, (CrC 4) haloalkyl, (C- ⁇ -C 4) haloalkoxy, nitro and oxo, in particular one or more times by radicals from the group halogen, (CrC 4) alkyl, (Ci -C 4) AI koxy, (CrC 4) haloalkyl and oxo, particularly by one or two (Ci-C4) alkyl substituted.
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl; The same applies to haloalkenyl and other halogen-substituted radicals.
  • An organic acid residue means a residue of an oxo acid or thioacid of the general formula
  • R is an organic residue
  • E is an atom from the group C, S, P,
  • R ' is independently a hydrogen atom, alkyl, haloalkyl, alkoxyalkyl or optionally aryl.
  • the organic acid radical is formally formed by separating a hydroxy group on the acid function, wherein the organic radical R in the acid can also be connected via one or more heteroatoms with the acid function:
  • alkylsulfonyl and alkylsulfinyl radicals such as (H 3 C) S (O) 2 , (F 3 C) S (O) 2 , P-ToIyIS (O) 2 , (H 3 C) S (O) (NH-Ii-C 4 H 9 ), (C 6 H 5 ) S (S) (O) or
  • Phosphonic acid derived radicals which radicals may be further esterified, for example -PO (OCH 3 ) 2 , (C 2 H 5 O) P (O) OH, (C 2 H 5 O) P (O) (SC 6 H 5 ), (H 3 CO) P (O) NH (C 6 H 5 ) or
  • alkylphosphinyl and alkylphosphonyl radicals e.g.
  • acyl examples include the radical -CO-R of a carboxylic acid HO-CO-R and radicals derived therefrom or the radical of carbonic acid monoesters or N-substituted carbamic acids and carbonates and their esters.
  • radicals may each be further substituted in the alkyl or phenyl part, for example in the alkyl part by one or more radicals from the group halogen, cyano, alkoxy, phenyl and phenoxy;
  • substituents in the phenyl moiety are the substituents already mentioned above generally for substituted phenyl.
  • Acyl is preferably an acyl radical in the strict sense, i. a residue of an organic acid in which the acid group is bonded directly to the carbon atom of an organic group, for example, alkanoyl such as formyl and acetyl, aroyl such as phenylcarbonyl, and other groups of saturated or unsaturated organic acids.
  • Aroyl means an aryl radical as defined above bonded through a carbonyl group, e.g. the benzoyl group.
  • the present invention also provides methods for the preparation of the compounds according to the invention.
  • the compounds of the invention may alternatively be prepared by various methods.
  • solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
  • Compounds of formula (I) may, for. Example by reaction of the corresponding halogen compounds (II) with the respective amine of formula (IM), optionally using an organic or inorganic base (eg., Triethylamine, pyridine, potassium carbonate, sodium carbonate).
  • an organic or inorganic base eg., Triethylamine, pyridine, potassium carbonate, sodium carbonate.
  • the reaction can be carried out in various solvents such as methanol, ethanol, dioxane, THF, dichloromethane, DMSO 1 DMF and water.
  • the reaction temperatures are generally between 20 ° C. and 180 ° C., depending on the amine used.
  • Compounds of formula (M) may, for. B. by reaction of the corresponding 4,6-dihalogen compounds (IV) with the respective alkali metal salt of the malononitrile.
  • the respective salts may, for. B. in situ by treatment of malononitrile with various bases such as n-butyl lithium, lithium diisopropylamide, sodium hydride or potassium carbonate at temperatures between -80 0 C and 80 0 C are generated.
  • the reaction is carried out in a temperature range between 0 0 C and 100 0 C, preferably in aprotic solvents such as THF, DMSO, DMF or dioxane.
  • Collections of compounds of the present invention which can be synthesized following the above reactions can also be prepared in a parallelized manner, which can be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
  • a number of commercially available devices may be used, for example Calypso reaction blocks (Calypso reaction blocks) from Barnstead International, Dubuque, Iowa 52004-0797, USA or Reaction Stations of the Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations of Perkin Elmar, Waltham, Massachusetts 02451, USA.
  • Calypso reaction blocks Calypso reaction blocks
  • chromatography equipment is available, for example the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
  • the listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed.
  • This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots.
  • Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
  • the preparation of compounds according to the invention can be carried out completely or partially by methods supported by solid phases.
  • individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin.
  • Solid phase assisted synthetic methods are well described in the literature, e.g. Barry A. Bunin in "The Combinatorial Index", Academic Press, 1998, and Combinatorial Chemistry - Synthesis, Analysis, Screening
  • the preparation according to the methods described herein provides compounds of the invention in the form of substance collections called libraries.
  • the present invention also provides libraries containing at least two compounds of the invention.
  • the compounds according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial harmful plants, which expel from rhizomes, rhizomes or other permanent organs are well detected by the active ingredients.
  • the present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied.
  • the compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process.
  • Monocotyledonous harmful plants of the genera Aegilops, Agropyron, Agrostis,
  • the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
  • the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous harmful plants, cultivated plants of economically important crops, such as dicotyledonous crops, for example of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus,
  • Glycine Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia or monocotyledonous cultures e.g. the genera Allium, Pineapple, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of the respective compound of the invention and their application rate only insignificantly or not at all damaged , For these reasons, the compounds according to the invention are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornamental plantings.
  • the compounds according to the invention (depending on their respective structure and the applied application rate) have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, such as be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.
  • the compounds according to the invention can also be employed for controlling harmful plants in crops of known or yet to be developed genetically modified plants.
  • the transgenic plants are usually distinguished by particular advantageous properties, for example by Resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties concern, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
  • Other special properties may include tolerance or resistance to abiotic stressors such as heat, cold, drought, salt and ultraviolet radiation.
  • cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables.
  • the compounds according to the invention can preferably be employed as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
  • new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants.
  • new plants with altered properties can be generated by genetic engineering techniques (see, for example, EP 0221044, EP 0131624).
  • genetic modifications of crops have been described in several instances to modify the starch synthesized in the plants (e.g., WO 92/011376 A, WO 92/014827 A,
  • transgenic crops which are resistant to certain herbicides of the type Glufosinate (cf., for example, EP 0 242 236 A, EP 0 242 246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0 257 993 A, US Pat. No. 5,013,659) or against combinations or mixtures of these herbicides by gene stacking "are resistant, such as transgenic crops such as corn or soybean with the trade name or the name Optimum TM GAT TM (Glyphosate ALS
  • Transgenic crops such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0 142 924 A, EP 0 193 259 A).
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins
  • transgenic crops with modified fatty acid composition WO 91/013972 A.
  • genetically engineered crops with new content or secondary substances e.g.
  • nucleic acid molecules can be used in any genetic manipulations.
  • nucleic acid molecules can be used in any genetic manipulations.
  • Plasmids are introduced which allow mutagenesis or a sequence change by recombination of DNA sequences.
  • standard methods can be used to exchange bases, to remove partial sequences, or to add natural or synthetic sequences.
  • adapters or linkers can be attached to the fragments, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
  • the production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
  • DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. Also possible is the use of DNA sequences encoding a high degree of homology to the ones
  • the synthesized protein may be located in any compartment of the plant cell.
  • the coding region can be linked to DNA sequences that ensure localization in a particular compartment.
  • sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
  • the expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
  • the transgenic plant cells can be whole by known techniques Plants are regenerated.
  • the transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants.
  • transgenic plants are available, the altered properties by
  • the compounds of the invention can be used in transgenic cultures which are resistant to growth factors, such as e.g. 2,4 D, dicamba or against herbicides containing essential plant enzymes, e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or Hydoxyphenylpyruvat Dioxygenases (HPPD) inhibit or resistant to herbicides from the group of sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogues, or against any combination of these agents resistant.
  • growth factors such as e.g. 2,4 D, dicamba or against herbicides containing essential plant enzymes, e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or Hydoxyphenylpyruvat Dioxygenases (HPPD)
  • ALS Acetolactate synthases
  • EPSP synthases glutamine
  • the compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Most preferably, the compounds of the invention in transgenic crops such. As corn or soybean with the trade name or the name Optimum TM GAT TM (Glyphosate ALS Tolerant) are used.
  • the invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds of the invention may e.g. be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations.
  • the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powders
  • EC emulsifiable concentrates
  • auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are for example, described in Watkins, Handbook of Insecticides Dust Diluents and Carriers, 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, “Solvents Guide”; 2 ⁇ d Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, “Encyclopedia of Surface Active Agents", Chem. Publ. Co.
  • Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance.
  • the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers).
  • organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers
  • fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxethylenesorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
  • Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solids e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. are already listed above for the other formulation types.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described, for example, in US Pat. listed above for the other formulation types.
  • EW Oil-in-water emulsions
  • Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
  • adhesives e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils
  • Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • spray drying for the preparation of plate, fluidized bed, extruder and spray granules, see for example methods in "Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration”, Chemicai and Engineering 1967, pages 147 ff; Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
  • the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
  • the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
  • Mixture formulations or in the tank mix are known, for example Active ingredients such as insecticides, fungicides, plant growth regulators or herbicides suitable.
  • Active ingredients such as insecticides, fungicides, plant growth regulators or herbicides suitable.
  • herbicides are those which are based on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase,
  • Photosystem I, photosystem II, protoporphyrinogen oxidase can be used, as e.g. from Weed Research 26 (1986) 441,445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and cited therein.
  • herbicides or plant growth regulators which can be combined with the compounds according to the invention are e.g. the following active ingredients (the compounds are denoted either by the "common name” according to the International Organization for Standardization (ISO) or the chemical name or with the code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
  • ISO International Organization for Standardization
  • Acetochlor Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen Sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim Sodium, Ametryn,
  • S1 a Compounds from the group of heterocyclic carboxylic acid derivatives: S1 a ) Compounds of the type of dichlorophenylpyrazoline-3-carboxylic acid (S1 a ), preferably compounds such as
  • S1 C derivatives of 1, 5-diphenylpyrazole-3-carboxylic acid (S1 C ), preferably compounds such as
  • S1 d compounds of the type of triazolecarboxylic acids (S1 d ), preferably compounds such as fenchlorazole (ethyl ester), ie
  • S2 a compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably (5-chloro-8-quinolinoxy) acetic acid (1-methylhexyl) ester ("cloquintocetmexyl") (S2-1), (5- Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyl oxy-butyl ester (S2- 3), (5-chloro-8-quinolinoxy) acetic acid 1 -allyloxy-prop-2-yl ester (S2-4),
  • S2 b compounds of the (5-chloro-8-quinolinoxy) malonic acid type (S2 b ), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester,
  • S3 Active substances of the dichloroacetamide type (S3), which are often used as pre-emergence safener (soil-active safener), such as. B.
  • Benoxacor (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
  • PPG-1292 N-allyl-N - [(1,3-dioxolan-2-yl) -methyl] -dichloroacetamide
  • AD-67 or "MON 4660” (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) of
  • TI-35 (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8),
  • RA 1 (CrC ⁇ JAlkyl which substituted by v A substituents from the group halogen, (Ci-C 4) alkoxy, (CrC ⁇ JHaloalkoxy and (CrC 4) alkylthio and in case of cyclic radicals, also by (CrC 4) alkyl and (CrC 4) haloalkyl is;
  • RA 2 is halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, CF 3;
  • VA is 0, 1, 2 or 3;
  • RB 1 , RB 2 independently of one another are hydrogen, (C 1 -C 6 ) -alkyl,
  • RB 3 is halogen, (C r C 4 ) alkyl, (C r C 4 ) haloalkyl or (Ci-C 4 ) Al koxy and m ⁇ is 1 or 2,
  • RB 1 cyclopropyl
  • RB 1 ethyl
  • RB 1 isopropyl
  • Rc 1 , Rc 2 independently of one another are hydrogen, (C 1 -C 8 ) alkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl,
  • Rc 3 is halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, CF 3 m c is 1 or 2;
  • active compounds from the class of 1, 2-dihydroquinoxalin-2-ones (S6) for example 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1-methyl-3- ( 2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxalin-2-one hydrochloride, 1- (2- Methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydro-quinoxalin-2-one as described in WO-A-2005/112630.
  • S6 2-dihydroquinoxalin-2-ones
  • S7 Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), for example methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid as described in WO-A-98/38856 are.
  • R D 1 is halogen, (Ci-C 4) alkyl, (dC 4) haloalkyl, (Ci-C 4) alkoxy,
  • RD 2 is hydrogen or (C r C 4 ) alkyl
  • RD 3 is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy is substituted; or their salts no is an integer from 0 to 2.
  • S9 Agents from the class of 3- (5-tetrazolylcarbonyl) -2-quinolones (S9), e.g. 1,2-Dihydro-4-hydroxy-1-ethyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No. 219479-18-2), 1, 2-dihydro-4-hydroxy-1 -methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS reg. no. 95855-00-8), as described in WO-A-1999/000020.
  • S9 1,2-Dihydro-4-hydroxy-1-ethyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No. 219479-18-2), 1, 2-dihydro-4-hydroxy-1 -methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS reg. no. 95855-00-8), as described in WO-A-1999/000020.
  • RE 1 is halogen, (C 1 -C 4) -alkyl 1 is methoxy, nitro, cyano, CF 3, OCF 3
  • YE, Z E independently of one another are O or S, n E is an integer from 0 to 4,
  • RE 3 is hydrogen or (d-C ⁇ JAlkyl mean.
  • S11) oxyimino compound type compounds (S11) known as seed dressings such as those described in US Pat. B.
  • Oxabetrinil ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed dressing safener for millet against damage by metolachlor,
  • Fluorofenim (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) -oxime) (S11-2) which was used as seed dressing Safener for millet is known against damage from metolachlor, and
  • Cyometrinil or “CGA-43089” ((Z) -cyanomethoxyimino (phenyl) acetonitrile) (S11-3), which is known as a seed dressing safener for millet against damage by metolachlor.
  • S12 active substances from the class of the isothiochromanones (S12), such as, for example, methyl - [(3-oxo-1H-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS Reg. No. 205121 -04- 6) (S12-1) and related compounds of WO-A-1998/13361. 513)
  • S12 isothiochromanones
  • Naphthalene anhydride (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as
  • Pretilachlor is known in sown rice
  • Some of the safeners are also known as herbicides and thus, in addition to the herbicidal action in harmful plants, at the same time also have a protective effect on the crop plants.
  • the weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20.
  • the safeners can be formulated analogously to the compounds according to the invention or mixtures thereof with further pesticides and can be provided and used as finished formulation or tank mixture with the compounds according to the invention.
  • the type of herbicide used u.a. varies the required application rate of the compounds of the invention. It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha.
  • the resulting product is suspended in 5 ml of concentrated ammonia solution and reacted for 8 hours at 150 ° C. in a closed vessel in a microwave oven. The solution is then in the
  • the substance is prepared analogously to the procedure for Ex. No. 174.
  • the starting material, 4,5,6-trichloro-2-phenylpyrimidine is obtained by literature methods: K. Findeisen, K. Wagner, Synthesis 1978, 40-42.
  • step B methylamine (40% solution in MeOH) is used and the reaction is carried out at 120 0 C for one hour in a microwave oven.
  • the substance is prepared analogously to the procedure for Ex. No. 371.
  • Ph phenyl
  • a dust is obtained by mixing 10 parts by weight of a compound according to the invention and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.
  • a wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of a compound according to the invention, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyltaurine sodium as wetting and dispersing agent, and grinded in a pin mill.
  • a dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound according to the invention with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71% by weight.
  • Mineral oil (boiling range, for example, about 255 to about 277 0 C) mixed and ground in a ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound according to the invention, 75 parts by weight of cyclohexanone as
  • a water-dispersible granule is obtained by reacting 75 parts by weight of a compound according to the invention, 10 parts by weight of calcium lignosulfonate,
  • a water-dispersible granules are also obtained by adding 25 parts by weight of a compound of the invention
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then treated as aqueous
  • compounds of the invention have good post-emergence herbicidal activity against a broad spectrum of weeds and weeds.
  • the compound No. 1 and other compounds from Tables 1 to 4 have very good herbicidal activity of at least 80% against harmful plants such as Matricaria inodora, Polygonum (Fallopia) convolvulus and Veronica persica postemergence at an application rate of 0.32 kg and less active substance per hectares.
  • compounds according to the invention leave gramineous crops such as barley, wheat, rye, millet, corn or rice undamaged after the postemergence process, even at high doses of active ingredient.
  • some substances also protect dicotyledonous crops such as soya, cotton, rapeseed, sugar beet or potatoes.
  • Some of the compounds according to the invention show a high selectivity and are therefore suitable postemergence for combating undesired plant growth in agricultural crops. Herbicidal action or crop plant compatibility in the pre-emergence
  • Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in sandy loam in wood fiber pots and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then treated as aqueous suspension or emulsion at a rate of application corresponding to 320 g / ha with a water application rate of 600 to 800 l / ha with addition of 0, 2% wetting agent applied to the surface of the cover soil.
  • compounds of the present invention have good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.
  • compounds Nos. 9 and other compounds shown in Tables 1 to 4 have very good herbicidal activity against harmful plants such as Sinapis alba, Avena fatua, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus and Alopecurus myosuroides preemergence at an application rate of 0.32 kg of active ingredient per hectare.
  • compounds according to the invention leave undigested dicotyledonous crops such as soybean, cotton, oilseed rape, sugar beets or potatoes in pre-emergence even at high doses of active ingredient. Some substances also protect graminaceous crops such as barley, wheat, rye, millet, corn or rice. Some of the compounds according to the invention show a high selectivity and are therefore suitable in the pre-emergence process for controlling undesired plant growth in agricultural crops. Table 6: Biological effects in pre-emergence

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Abstract

The invention relates to compounds of the formula (I) and the N-oxides, tautomers, and agrochemically compatible salts thereof. The invention further relates to a method for the production thereof, and to the use thereof as herbicide and plant growth regulators, particularly as a herbicide for selectively treating weeds in commercial plant cultures.

Description

PyτiiTιidin-4-yiρröpanuinitrii-Derivate, Verfahren zu deren Hersteiiung sowie deren Verwendung als Herbizide und Pflanzenwachstumsregulatoren PyτiiTιidin-4-yiρröpanuinitrii derivatives, processes for their preparation and their use as herbicides and plant growth regulators
Die vorliegende Erfindung betrifft neue, herbizid wirksame Pyrimidin-4- ylpropandinitril-Derivate sowie Verfahren zu deren Herstellung. Weiterer Gegenstand der vorliegenden Erfindung ist deren Verwendung als Herbizid, insbesondere als Herbizid zur selektiven Bekämpfung von Schadpflanzen in Nutzpflanzenkulturen, und als Pflanzenwachstumsregulator allein oder in Kombination mit Safenern und/oder in Mischung mit anderen Herbiziden.The present invention relates to novel, herbicidally active pyrimidin-4-ylpropandinitrile derivatives and to processes for their preparation. Another object of the present invention is its use as a herbicide, in particular as a herbicide for the selective control of harmful plants in crops, and as a plant growth regulator alone or in combination with safeners and / or in admixture with other herbicides.
Aus verschiedenen Schriften ist bekannt, dass substituierte Pyrimidin-Derivate herbizide bzw. schädlingsbekämpfende Eigenschaften besitzen (siehe beispielsweise WO 2005/063721 , WO 2007/082076, sowie C. Lamberth, Heterocycles 2006, 68, 3, 561-603 und dort zitierte Literatur). Die aus den oben genannten Schriften bekannten Wirkstoffe weisen bei ihrer Anwendung jedoch Nachteile auf, z. B. dass sie (a) keine oder aber eine nur unzureichende herbizide Wirkung gegen Schadpflanzen, (b) ein zu geringes Spektrum der bekämpften Schadpflanzen, oder (c) eine zu geringe Selektivität in Nutzpflanzenkulturen besitzen.It is known from various publications that substituted pyrimidine derivatives have herbicidal or pest-controlling properties (see, for example, WO 2005/063721, WO 2007/082076, and C. Lamberth, Heterocycles 2006, 68, 3, 561-603 and literature cited therein). , However, the active ingredients known from the above-mentioned publications have disadvantages in their application, for. B. that they have (a) no or only insufficient herbicidal activity against harmful plants, (b) a too low a spectrum of the contested harmful plants, or (c) a too low selectivity in crops.
Aus EP 0 136 976 A bekannt sind 2-Phenyl-substituierte Pyrimidine, welche alsEP 0 136 976 A discloses 2-phenyl-substituted pyrimidines which are known as
Wachstumsregulatoren eingesetzt werden. Eine herbizide Wirkung wird jedoch nicht offenbart, ebensowenig wie das erfindungsgemäße Substitutionsmuster.Growth regulators are used. However, a herbicidal action is not disclosed, any more than the substitution pattern according to the invention.
DE 25 20 381 A1 offenbart ebenfalls Pyrimidin-basierte Pflanzenwachstumsregulatoren, welche allerdings nur aliphatische Kohlenwasserstoff-Substituenten am Pyrimidin tragen.DE 25 20 381 A1 likewise discloses pyrimidine-based plant growth regulators, which however only carry aliphatic hydrocarbon substituents on pyrimidine.
Es ist deshalb wünschenswert, chemische Wirkstoffe bereitzustellen, die mit Vorteilen als Herbizide oder Pflanzenwachstumsregulatoren eingesetzt werden können.It is therefore desirable to provide chemical agents which are used with advantage as herbicides or plant growth regulators can.
Es wurde nun überraschend gefunden, dass bestimmte substituierte Pyrimidin-4- yipropandinitril-Derivate gute herbizide Wirkung und gleichzeitig hohe Verträglichkeit gegenüber Nutzpflanzen aufweisen. Ein Gegenstand der vorliegenden Erfindung sind daher Verbindungen der Formel (I) und deren N-Oxide und agrochemisch geeignete Salze,It has now surprisingly been found that certain substituted pyrimidine-4-yipropandinitrile derivatives have good herbicidal activity and at the same time high compatibility with useful plants. An object of the present invention are therefore compounds of formula (I) and their N-oxides and agrochemically suitable salts,
worin die Reste die folgende Bedeutung aufweisen:wherein the radicals have the following meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (CrC6)Alkyl, (Cr C6)Haloalkyl, (CrC4)Hydroxyalkyl, (C2-C4)Alkoxyalkyl, (C2-C4)Haloalkoxyalkyl,R 1 is phenyl, optionally substituted by 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 4 ) hydroxyalkyl, (C 2 - C 4 ) alkoxyalkyl, (C 2 -C 4 ) haloalkoxyalkyl,
(C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C2-C4)Alkinyl, (C3-C4)Haloalkinyl, Hydroxy, (CrC4)AIkOXy, (CrC4)Haloalkoxy, (C2-C4)Alkenyloxy, (C2-C4)Haloalkenyloxy, (C2-C4)Alkinyloxy, (C3-C4)Haloalkinyloxy, (CrC4)Alkylthio, (d-C4)Haloalkylthio, (CrC4)Alkylsulfinyl, (CrC4)Haloalkylsulfinyl, (CrC4)Alkylsulfonyl, (C1- C4)Haloalkylsulfonyl, (C2-C4)Alkenylthio, (C2-C4)Haloalkenylthio, (C2-(C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl, (C 2 -C 4) alkynyl, (C 3 -C 4) haloalkynyl, hydroxy, (CrC 4) -alkoxy, (CrC 4) haloalkoxy, (C 2 -C 4) alkenyloxy, (C 2 -C 4) haloalkenyloxy, (C 2 -C 4) alkynyloxy, (C 3 -C 4) Haloalkinyloxy, (C r C4) alkylthio, (dC 4) haloalkylthio, (CrC 4 ) alkylsulfinyl, (CrC 4 ) haloalkylsulfinyl, (C r C 4 ) alkylsulfonyl, (C 1 - C 4 ) haloalkylsulfonyl, (C 2 -C 4 ) alkenylthio, (C 2 -C 4 ) haloalkenylthio, (C 2 -
C4)Alkenylsulfinyl, (C2-C4)Haloalkenylsulfinyl, (C2-C4)Alkenylsulfonyl, (C2- C4)Haloalkenylsulfonyl, (C2-C4)Alkinylthio, (C3-C4)Haloalkinylthio, (C3- C4)Alkinylsulfinyl, (C3-C4)Haloalkinylsulfinyl, (C3-C4)Alkinylsulfonyl, (C3- C4)Haloalkinylsulfonyl, (CrC6)Alkylamino, (C2-C8)Dialkylamino, (C2- C6)Alkylcarbonyl, (C2-C6)Alkoxycarbonyl, (C2-C6)Alkylaminocarbonyl, (C3-C 4) alkenylsulfinyl, (C 2 -C 4) Haloalkenylsulfinyl, (C 2 -C 4) alkenylsulphonyl, (C 2 - C 4) Haloalkenylsulfonyl, (C 2 -C 4) alkynylthio, (C 3 -C 4) Haloalkinylthio, (C 3 - C 4) alkynylsulfinyl, (C 3 -C 4) Haloalkinylsulfinyl, (C 3 -C 4) alkynylsulfonyl, (C 3 - C 4) Haloalkinylsulfonyl, (CrC 6) alkylamino, (C 2 -C 8) dialkylamino , (C 2 - C 6) alkylcarbonyl, (C 2 -C 6) alkoxycarbonyl, (C 2 -C 6) alkylaminocarbonyl, (C 3 -
CsJDialkylaminocarbonyl, (C3-C6)Trialkylsilyl, Phenyl, Phenoxy oder einen 5- oder 6-gliedrigen heteroaromatischen Ring, jeder Phenyl-Ring, Phenoxy-Ring oder 5-oder 6-gliedrige heteroaromatische Ring optional substituiert mit 1-3 Substituenten unabhängig voneinander ausgewählt aus R28; oder zwei benachbarte Reste Rx bilden gemeinsam eine GruppeCsDialkylaminocarbonyl, (C 3 -C 6 ) trialkylsilyl, phenyl, phenoxy or a 5- or 6-membered heteroaromatic ring, each phenyl ring, phenoxy ring or 5- or 6-membered heteroaromatic ring optionally substituted with 1-3 substituents independently selected from R 28 ; or two adjacent radicals R x together form a group
-OCH2O-, -CH2CH2O-, -OCH2CH2O-, -OCH(CH3)O-, -OC(CH3)2O-, -OCF2O-,-OCH 2 O-, -CH 2 CH 2 O-, -OCH 2 CH 2 O-, -OCH (CH 3 ) O-, -OC (CH 3 ) 2 O-, -OCF 2 O-,
-CF2CF2O-, -OCF2CF2O- oder -CH=CH-CH=CH-; oder-CF 2 CF 2 O-, -OCF 2 CF 2 O- or -CH = CH-CH = CH-; or
(CrC6)-Alkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander Halogen, (C2-C6)Alkenyl, (C2-C6)Haloalkenyl, (Ci-C3)AIkOXy, (Cr C2)Haloalkoxy, (d-C3)Alkylthio, (CrC2)Haloalkylthio oder gegebenenfalls substituiertes Aryl bedeuten; oder(C 1 -C 6 ) -alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) -haloalkenyl, (C 1 -C 3 ) -alkoxy, (Cr C 2 ) haloalkoxy, (dC 3 ) alkylthio, (CrC 2 ) haloalkylthio or optionally substituted aryl; or
(C2-Cβ)-Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander Halogen, (CrC6)Alkyl, (CrC6)Haloalkyl, (C1-C3)AIkOXy, (G1- C2)Haloalkoxy, (CrC3)Alkylthio oder (CrC2)Haloalkylthio bedeuten;(C 2 -Cβ) alkenyl, optionally substituted by 1-3 radicals R z, which are independently halo, (C r C6) alkyl, (CrC 6) haloalkyl, (C 1 -C 3) -alkoxy, (G 1 - C 2 ) haloalkoxy, (C r C 3 ) alkylthio or (C r C 2 ) haloalkylthio;
R2 ist H, F, Cl, Br, I, CN, NO2, OR5, SR6 oder N(R7)R8; worin R5 H, (CrC4)Alkyl oder (CrC3)Haloalkyl ist, R6 H, (CrC4)Alkyl oder (CrC3)Haloalkyl ist und R7 und R8 unabhängig voneinander H oder (Ci-C4)Alkyl sind;R 2 is H, F, Cl, Br, I, CN, NO 2 , OR 5 , SR 6 or N (R 7 ) R 8 ; wherein R 5 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl, R 6 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl and R 7 and R 8 are independently H or (C 1 -C 4 ) alkyl;
R3 ist H, (CrC4)Alkyl optional substituiert mit 1-2 Resten R9, (C2-C4)AI kenyl optional substituiert mit 1-2 Resten R10, oder (C2-C4)Alkinyl optional substituiert mit 1-2 Resten R11; oder R3 ist C(=O)R12, NO2, OR13, S(O)2R14, N(R15)R16 oderR 3 is H, (C r C 4 ) alkyl optionally substituted with 1-2 radicals R 9 , (C 2 -C 4 ) alkylene optionally substituted with 1-2 radicals R 10 , or (C 2 -C 4 ) alkynyl optionally substituted with 1-2 radicals R 11 ; or R 3 is C (= O) R 12 , NO 2 , OR 13 , S (O) 2 R 14 , N (R 15 ) R 16 or
N=C(R17)R18;N = C (R 17 ) R 18 ;
R4 ist H, (CrC4)Alkyl optional substituiert mit 1-2 Resten R9, oder C(=O)R12; oder R3 und R4 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- oderR 4 is H, (C r C 4 ) alkyl optionally substituted with 1-2 radicals R 9 , or C (= O) R 12 ; or R 3 and R 4 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, -CH 2 CH = CHCH 2 - or
-(CH2)2O(CH2)2-, jede Gruppe optional substituiert mit 1-2 Resten R19; oder R3 und R4 bilden gemeinsam eine Gruppe =C(R20)N(R21)R22 oder =C(R23)OR24;- (CH 2 ) 2 O (CH 2 ) 2 -, each group optionally substituted with 1-2 R 19 radicals; or R 3 and R 4 together form a group = C (R 20) N (R 21) R 22 or = C (R 23) OR 24;
dabei ist jeder Rest R9, R10 und R11 unabhängig voneinander Halogen, (Creach radical R 9 , R 10 and R 11 is independently halogen, (Cr
C3)AIkOXy1 (CrC3)Haloalkoxy, (d-C3)Alkylthio, (Ci-C3)Haloalkylthio, Amino, (Ci-C3)Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl; R12 ist jeweils unabhängig voneinander H, (d-C4)Alkyl, (CrC3)Haloalkyl, (CrC 3) -alkoxy 1 (C r C 3) haloalkoxy, (dC 3) alkylthio, (Ci-C 3) haloalkylthio, amino, (Ci-C 3) alkylamino, (C 2 -C 4) dialkylamino, or (C 2 - C 4 ) alkoxycarbonyl; R 12 is each independently H, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (Cr
C4)AIkOXy, Phenyl, Phenoxy oder Benzyloxy; R13 ist H, (CrC4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26; R14 ist (CrC4)Alkyl oder (Ci-C3)Haloalkyl; R15 ist H, (CrC4)Alkyl oder C(=O)R27; R16 ist H oder (CrC4)Alkyl;C 4 ) AIkOXy, phenyl, phenoxy or benzyloxy; R 13 is H, (C r C 4 ) alkyl, (CrC 3 ) haloalkyl or CHR 25 C (O) OR 26 ; R 14 is (C r C 4 ) alkyl or (Ci-C 3 ) haloalkyl; R 15 is H, (C r C 4 ) alkyl or C (= O) R 27 ; R 16 is H or (C r C 4 ) alkyl;
R17 ist H, (CrC4)Alkyl oder Phenyl optional substituiert mit 1-3 Resten, welche voneinander unabhängig CH3, Cl oder OCH3 bedeuten;R 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals independently of one another representing CH 3 , Cl or OCH 3 ;
R18 ist H oder (Ci-C4)Alkyl; oder R17 und R18 bilden gemeinsam eine GruppeR 18 is H or (Ci-C 4) alkyl; or R 17 and R 18 together form a group
-(CH2)4- oder -(CH2)S-; R19 ist jeweils unabhängig voneinander Halogen, (C-ι-C3)Alkyl, (Ci -C3)AIkOXy,- (CH 2 ) 4 - or - (CH 2 ) S -; R 19 is in each case independently halogen, (C 1 -C 3 ) -alkyl, (C 1 -C 3 ) -alkoxy,
(CrC3)Haloalkoxy, (CrC3)Alkylthio, (Ci-C3)Haloalkylthio, Amino, (G1- C3)Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl;(CrC 3 ) haloalkoxy, (C r C 3 ) alkylthio, (C 1 -C 3 ) haloalkylthio, amino, (G 1 - C 3 ) alkylamino, (C 2 -C 4 ) dialkylamino or (C 2 -C 4 ) alkoxycarbonyl ;
R20 ist H oder (Ci-C4)Alkyl; R21 und R22 sind unabhängig voneinander H oder (CrC4)Alkyl; oder R21 und R22 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- oderR 20 is H or (C 1 -C 4 ) alkyl; R 21 and R 22 are independently H or (C 1 -C 4 ) alkyl; or R 21 and R 22 together form a group - (CH 2) 4 -, - (CH 2) 5 -, -CH 2 CH = CHCH 2 -, or
-(CH2)2O(CH2)2-; R23 ist H oder (CrC4)Alkyl; R24 ist (CrC4)Alkyl; R25 ist H, (Ci-C4)Alkyl, (CrC3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder- (CH 2 ) 2 O (CH 2 ) 2 -; R 23 is H or (C r C 4 ) alkyl; R 24 is (C r C 4 ) alkyl; R 25 is H, (Ci-C 4 ) alkyl, (C r C 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or
Benzyloxy;benzyloxy;
R26 ist H, (CrC4)Alkyl oder (CrC4)Alkoxy; R27 ist H, (C1-C4) Alkyl oder Benzyl; undR 26 is H, (C r C 4 ) alkyl or (C r C 4 ) alkoxy; R 27 is H, (C 1 -C 4 ) alkyl or benzyl; and
R28 ist jeweils unabhängig voneinander Halogen, Cyano, Nitro, (d-CβJAlkyl, (CrR 28 is each independently halogen, cyano, nitro, (C 1 -C 6 alkyl, (Cr
C6)Haloalkyl, (C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C3-C4)Alkinyl, (C3-C 6) haloalkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl, (C 3 -C 4) alkynyl, (C 3 -
C4)Haloalkinyl, (CrC4)Alkoxy, (CrC4)Haloalkoxy, (CrC4)Alkylthio, (Cr C 4 ) haloalkynyl, (C r C 4 ) alkoxy, (C r C 4 ) haloalkoxy, (C r C 4 ) alkylthio, (C r
C4)Haloalkylthio, (CrC4)Alkylsulfinyl, (CrC4)Alkylsulfonyl, (CrC4)Alkylamino, (C2-C8)Dialkylamino, (C2-C4)Alkylcarbonyl, (C2-C6)Alkoxycarbonyl, (C2-C 4) haloalkylthio, (C r C4) alkylsulfinyl, (C r C 4) alkylsulfonyl, (C r C4) alkylamino, (C 2 -C 8) dialkylamino, (C 2 -C 4) alkylcarbonyl, (C 2 -C 6 ) alkoxycarbonyl, (C 2 -
C6)Alkylaminocarbonyl, (Cs-CβJDialkylaminocarbonyl oder (C3-C6)Trialkylsilyl.C 6 ) alkylaminocarbonyl, (Cs-Cβ-dialkylaminocarbonyl or (C 3 -C 6 ) -trialkylsilyl.
Dabei ist bei den genannten Resten stets die Gesamtzahl an C-Atomen angegeben, z.B. ist ein Dimethylaminocarbonyl-Rest ein C3-ReSt.In this case, the total number of C atoms is always given in the radicals mentioned, for example, a dimethylaminocarbonyl radical is a C 3 -ReSt.
Bevorzugt sind Verbindungen der Formel (I), worin die Reste folgende Bedeutung aufweisen: R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (C1-C6)AIKyI, (C1- C6)Haloalkyl, (C2-C4)Alkoxyalkyl, (C2-C4)Haloalkoxyalkyl, (C2-C4)Alkenyl, (C2- C4)Haloalkenyl, (C2-C4)Alkinyl, (C3-C4)Haloalkinyl, Hydroxy, (C1-C4)AIkOXy, (C1- C4)Haloalkoxy, (CrC4)Alkylthio, (CrC4)Haloalkylthio, (CrC4)Alkylsulfinyl, (C1-Preference is given to compounds of the formula (I) in which the radicals have the following meanings: R 1 is phenyl, optionally substituted by 1-3 R x radicals, which independently represent halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 4) alkoxyalkyl, (C 2 -C 4) haloalkoxyalkyl, (C 2 -C 4) alkenyl, (C 2 - C 4) haloalkenyl, (C 2 -C 4) alkynyl, (C 3 -C 4) haloalkynyl, hydroxy , (C 1 -C 4) -alkoxy, (C 1 - C 4) haloalkoxy, (CrC 4) alkylthio, (C r C4) haloalkylthio, (C r C4) alkylsulfinyl, (C 1 -
C4)Alkylsulfonyl, (CrC6)Alkylannino, (C2-C8)Dialkylamino, -OCH2O-, -CH2CH2O-, -OCH2CH2O-, -OCH(CH3)O-, -OC(CH3)2O-, -OCF2O-, -CF2CF2O- oder - OCF2CF2O-, wobei die acht letztgenannten Substituenten jeweils durch zwei benachbarte Rx gebildet werden; oderC 4 ) alkylsulfonyl, (C 1 -C 6 ) alkylannino, (C 2 -C 8 ) dialkylamino, -OCH 2 O-, -CH 2 CH 2 O-, -OCH 2 CH 2 O-, -OCH (CH 3 ) O- , -OC (CH 3 ) 2 O-, -OCF 2 O-, -CF 2 CF 2 O- or -OCF 2 CF 2 O-, wherein the eight latter substituents are each formed by two adjacent R x ; or
(C-i-CβJAlkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (C2-C6)Alkenyl, (C2-C6)Haloalkenyl, (C1- C3)AIkOXy, (C1-C2)HaIOaIkOXy, (CrC2)Haloalkylthio oder gegebenenfalls substituiertes Phenyl; oder(C 1 -C 6 ) alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy, (C r C 2 ) haloalkylthio or optionally substituted phenyl; or
(C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (Ci-Cβ)Alkyl, (CrC6)Haloalkyl, (C1-C3)AIkOXy, (C1-C2)HaIOaIkOXy, (CrC3)Alkylthio oder (CrC2)Haloalkylthio;(C 2 -C 6 ) alkenyl, optionally substituted by 1-3 radicals R z , which independently of one another are halogen, (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -haloalkyl, (C 1 -C 3 ) -alkoxy, (C 1 -C 2 ) haloalkoxy, (C r C 3 ) alkylthio or (C r C 2 ) haloalkylthio;
R2 ist H, F, Cl, Br, I, CN oder NO2;R 2 is H, F, Cl, Br, I, CN or NO 2 ;
R3 ist H, (CrC4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, C(=O)R12, OR13, N(R15)R16 oder N=C(R17)R18;R 3 is H, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, C (= O) R 12 , OR 13 , N (R 15 ) R 16 or N = C (R 17 ) R 18 ;
R4 ist H oder (CrC4)Alkyl, optional substituiert mit 1-2 Resten R9, oder C(=O)R12; oderR 4 is H or (C r C 4 ) alkyl optionally substituted with 1-2 radicals R 9 , or C (= O) R 12 ; or
R3 und R4 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -(CH2)2O(CH2)2- oderR 3 and R 4 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 O (CH 2 ) 2 - or
=C(R20)N(R21)R22;= C (R 20 ) N (R 21 ) R 22 ;
dabei ist jeder Rest R9, R10 und R11 unabhängig voneinander Halogen, (C1- C3)Alkoxy, (C1-C3)HaIOaIkOXy, (CrC3)Alkylthio, (CrC3)Haloalkylthio, Amino,thereby, each R 9, R 10 and R 11 are each independently halogen, (C 1 - C 3) alkoxy, (C 1 -C 3) HaIOaIkOXy, (C r C 3) alkylthio, (CrC 3) haloalkylthio, amino,
(CrC^Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl; R12 ist jeweils unabhängig voneinander H, (CrC4)Alkyl, (CrC3)Haloalkyl, (C1- C4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy; R13 ist H, (Ci-C4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26; R15 ist H, (Ci-C4)Alkyl oder C(=O)R27; R16 ist H oder (CrC4)Alkyl; R17 ist H, (CrC4)Alkyl oder Phenyl optional substituiert mit 1-3 Resten, welche voneinander unabhängig CH3, Cl oder OCH3 bedeuten; R18 ist H oder (d-C4)Alkyl; oder R17 und R18 bilden gemeinsam eine Gruppe(CrC ^ alkylamino, (C 2 -C 4) dialkylamino, or (C 2 -C 4) alkoxycarbonyl; R 12 is independently H, (CrC 4) alkyl, (CrC 3) haloalkyl, (C 1 - C 4 ) alkoxy, phenyl, phenoxy or benzyloxy; R 13 is H, (C 1 -C 4 ) alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O) OR 26 ; R 15 is H, (C 1 -C 4 ) alkyl or C (= O) R 27 ; R 16 is H or (C r C 4 ) alkyl; R 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals independently of one another representing CH 3 , Cl or OCH 3 ; R 18 is H or (C 1 -C 4 ) alkyl; or R 17 and R 18 together form a group
-(CH2)4- oder -(CH2)S-; R20 ist H oder (CrC4)Alkyl; R21 und R22 sind unabhängig voneinander H oder (Ci-C4)Alkyl; oder R21 and R22 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- oder- (CH 2 ) 4 - or - (CH 2 ) S-; R 20 is H or (C r C 4 ) alkyl; R 21 and R 22 are independently H or (Ci-C 4 ) alkyl; or R 21 and R 22 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, -CH 2 CH = CHCH 2 - or
-(CH2)2O(CH2)2-; R25 ist H, (d-C4)Alkyl, (CrC3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder- (CH 2 ) 2 O (CH 2 ) 2 -; R 25 is H, (dC 4 ) alkyl, (CrC 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or
Benzyloxy; und R26 ist H, (d-C4)Alkyl oder (CrC4)Alkoxy.benzyloxy; and R 26 is H, (dC 4) alkyl or (C r C 4) alkoxy.
Besonders bevorzugt sind Verbindungen der Formel (I), worin die Reste folgende Bedeutung aufweisen:Particular preference is given to compounds of the formula (I) in which the radicals have the following meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (Ci-Cβ)Alkyl, (CrR 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently represent halogen, carboxyl, cyano, nitro, (Ci-Cβ) alkyl, (Cr
C6)Haloalkyl, (CrC4)Alkoxy, (Ci-C4)Haloalkoxy, (Ci-C6)Alkylamino, (C2- CsJDialkylamino,C 6) haloalkyl, (C r C 4) alkoxy, (Ci-C 4) haloalkoxy, (Ci-C 6) alkylamino, (C 2 - CsJDialkylamino,
-OCH2O-, -OCH2CH2O- oder -OCH(CH3)O-, wobei die drei letztgenannten Substituenten jeweils durch zwei benachbarte Rx gebildet werden; oder (d-CβJAlkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (CrC3)Alkoxy, (CrC2)Haloalkoxy oder unsubstituiertes oder durch ein oder mehrere Halogene substituiertes Phenyl; oder-OCH 2 O-, -OCH 2 CH 2 O- or -OCH (CH 3 ) O-, wherein the last three substituents are each formed by two adjacent R x ; or (C 1 -C 6 alkyl optionally substituted with 1-3 radicals R y , which independently of one another are halogen, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy or phenyl which is unsubstituted or substituted by one or more halogens;
(C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (CrCβJAlkyl, (Ci-C6)Haloalkyl, (Ci-C3)Alkoxy oder (CrC2)Haloalkoxy; R2 ist F, Cl, Br, I oder NO2; R3 ist H, (C1-C4)AIkYl, (C2-C4)AI kenyl, C(=O)R12, worin R12 H, (CrC4)Alkyl, (C1- C3)Haloalkyl, (C1-C4)AIkOXy, Phenyl, Phenoxy oder Benzyloxy ist, oder OR13, worin R13 H, (CrC4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26 ist, worin R25 H, (CrC4)Alkyl, (C-i-C3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy ist, und R26 H, (CrC4)Alkyl oder (CrC4)Alkoxy ist;(C 2 -C 6) alkenyl optionally substituted by 1-3 radicals R z, which independently of one another, halogen (CrCβJAlkyl, (Ci-C 6) haloalkyl, (Ci-C 3) alkoxy or (C r C 2) Haloalkoxy; R 2 is F, Cl, Br, I or NO 2 ; R 3 is H, (C 1 -C 4) -alkyl, (C 2 -C 4) -alkenyl AI, C (= O) R 12 wherein R 12 is H, (C r C4) alkyl, (C 1 - C 3 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy or benzyloxy, or OR 13 , wherein R 13 is H, (C r C 4 ) alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O ) OR 26 is where R 25 is H, (C r C 4 ) alkyl, (CiC 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or benzyloxy, and R 26 is H, (C r C 4 ) Alkyl or (C r C 4 ) alkoxy;
R4 ist H oder (CrC4)Alkyl; oderR 4 is H or (C r C 4 ) alkyl; or
R3 und R4 bilden gemeinsam eine Gruppe -(CH2)2O(CH2)2-.R 3 and R 4 together form a group - (CH 2 ) 2 O (CH 2 ) 2 -.
Ganz besonders bevorzugt sind Verbindungen der Formel (I), worin die Reste folgende Bedeutung aufweisen:Very particular preference is given to compounds of the formula (I) in which the radicals have the following meanings:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (C1- C6)Haloalkyl, (C1-C4)AIkOXy, (CrC4)Haloalkoxy; oder (CrC6)Alkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (C1-C3)AIkOXy, (CrC2)Haloalkoxy oder unsubstituiert.es oder durch ein Halogen substituiertes Phenyl ; oder (C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (C1-C6)AIkYl, (CrC6)Haloalkyl, (C1-C3)AIkOXy oder (CrC2)Haloalkoxy; R2 ist F, Cl, Br, I oder NO2;R 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) haloalkyl, (C 1 -C 4 ) alkoxy, (C r C 4 ) haloalkoxy; or (C 1 -C 6 ) alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy or unsubstituted or substituted by a halogen; or (C 2 -C 6) alkenyl optionally substituted by 1-3 radicals R z, which independently of one another, halogen (C 1 -C 6) -alkyl, (CrC 6) haloalkyl, (C 1 -C 3) -alkoxy or (CrC 2 ) haloalkoxy; R 2 is F, Cl, Br, I or NO 2 ;
R3 ist H, (CrC4)Alkyl, (C2-C4)AI kenyl, C(=O)R12, worin R12 H, (CrC4)Alkyl, (C1- C3)Haloalkyl oder (C1-C4)AIkOXy ist, oder OR13, worin R13 H, (CrC4)Alkyl oder (CrC3)Haloalkyl ist; und R4 ist H oder (CrC4)Alkyl.R 3 is H, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl, C (= O) R 12 , wherein R 12 is H, (C r C 4 ) alkyl, (C 1 -C 3 ) Haloalkyl or (C 1 -C 4 ) alkoxy, or OR 13 , wherein R 13 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl; and R 4 is H or (C r C 4 ) alkyl.
Insbesondere bevorzugt sind Verbindungen der Formel (I), worin die Reste folgendeParticular preference is given to compounds of the formula (I) in which the radicals have the following meanings
Bedeutung aufweisen:Have meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Nitro, (CrCβJAlkyl, (C-i-CβJHaloalkyl, (C1-C4)AIkOXy; oderR 1 is phenyl, optionally substituted with 1-3 R x radicals, which independently represent halogen, carboxyl, nitro, (C 1 -C 6 alkyl, (C 1 -C 6 haloalkyl, (C 1 -C 4 ) alkoxy;
(CrC6)Alkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, Phenyl oder 4-Halogen-Phenyl; R2 ist F, Cl, Br oder NO2;(C 1 -C 6 ) alkyl, optionally substituted with 1-3 radicals R y , which independently represent halogen, phenyl or 4-halo-phenyl; R 2 is F, Cl, Br or NO 2 ;
R3 ist H oder (CrC4)Alkyl; undR 3 is H or (C r C 4 ) alkyl; and
R4 ist H oder (CrC4)Alkyl.R 4 is H or (C r C 4 ) alkyl.
Die Verbindungen der Formel (I) können durch Wasserstoffverschiebung Tautomere bilden, welche ebenfalls Gegenstand der vorliegenden Erfindung sind. So können beispielsweise die Pyrimidin-4-ylpropandinitril-Derivate (I) auch als Pyrimidin-4(3/-/)-ylidenpropandinitrile (Ia) oder als Pyrimidin-4(7/-/)- ylidenpropandinitrile (Ib) vorliegen, wobei erfindungsgemäß sämtliche Tautomere umfasst sind, insbesondere die Formen (I), (Ia) und (Ib).The compounds of the formula (I) can form tautomers by hydrogen displacement, which are also the subject of the present invention. Thus, for example, the pyrimidin-4-ylpropandinitrile derivatives (I) can also be present as pyrimidine-4 (3 / - /) - ylidene-divinitriles (Ia) or as pyrimidine-4 (7 / - /) - ylidene-divinitriles (Ib), according to the invention all tautomers are included, in particular the forms (I), (Ia) and (Ib).
( I ) ( Ia ) ( Ib )(I) (Ia) (Ib)
Die Verbindungen der Formel (I) können je nach Art und Verknüpfung derThe compounds of formula (I) may, depending on the nature and linkage of
Substituenten als Stereoisomere vorliegen. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere, geometrische Isomere und Atropisomere und deren Gemische sind alle von Formel (I) umfasst.Substituents exist as stereoisomers. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, geometric isomers and atropisomers, and mixtures thereof are all encompassed by formula (I).
Sind beispielsweise eine oder mehrere Alkenylgruppen vorhanden, so können Diastereomere (Z- und E-Isomere) auftreten. Sind beispielsweise ein oder mehrere asymmetrische Kohlenstoffatome ( = asymmetrisch substituierte Kohlenstoffatome) vorhanden und/oder asymmetrische Schwefelatome in Form von Sulfoxiden, die in zwei enantiomeren Formen existieren können, so können Enantiomere undIf, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) can occur. For example, if one or more asymmetric carbon atoms (= asymmetrically substituted carbon atoms) are present and / or asymmetric sulfur atoms in the form of sulfoxides, which may exist in two enantiomeric forms, enantiomers and
Diastereomere auftreten. Stereoisomere lassen sich aus den bei der Herstellung anfallenden Gemischen nach üblichen Trennmethoden, beispielsweise durch chromatographische Trennverfahren, isolieren. Ebenso können Stereoisomere durch Einsatz stereoselektiver Reaktionen unter Verwendung optisch aktiver Ausgangs- und/oder Hilfsstoffe selektiv hergestellt werden. Die Erfindung betrifft somit auch alle Stereoisomeren, die von der allgemeinen Formel (I) umfasst werden, auch wenn sie nicht mit ihrer spezifischen Stereoform angegeben sind, und deren Gemische.Diastereomers occur. Stereoisomers can be prepared from the mixtures obtained in the preparation by conventional separation methods, for example by chromatographic separation process, isolate. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which are encompassed by the general formula (I), even if they are not specified with their specific stereoform, and mixtures thereof.
Die Verbindungen der Formel (I) können agrochemisch geeignete Salze bilden. Salzbildung kann in bekannter Weise, z. B. durch Einwirkung einer Base auf solche Verbindungen der Formel (I) erfolgen, die ein acides Wasserstoffatom tragen, z.B. im Falle dass R1 eine OH-Gruppe oder eine Sulfonamid-Gruppe -NHSO2- enthält. Eine Salzbildung kann ebenfalls durch das Einwirken einer Base auf CH-acide Verbindungen, wie (substituierte) Propandinitrile, erfolgen. Geeignete Basen sind beispielsweise organische Amine, wie Trialkylamine, Morpholin, Piperidin oder Pyridin sowie Ammoniak, Ammonium-, Alkali- oder Erdalkalimetallhydroxide, -carbonate und -hydrogencarbonate, insbesondere Natrium- und Kaliumhydroxid, Natrium- und Kaliumcarbonat und Natrium- und Kaliumhydrogencarbonat. Diese Salze sind Verbindungen, in denen der acide Wasserstoff durch ein für die Landwirtschaft geeignetes Kation ersetzt wird, beispielsweise Metallsalze, insbesondere Alkalimetallsalze oder Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, oder auch Salze mit organischen Aminen oder Ammoniumsalze, zum Beispiel mit Ammoniumionen der Formel [NRR'R"R"']\ worin R, R', R" und R'" jeweils unabhängig voneinander H oder einen organischen Rest, insbesondere (C-ι-C6)Alkyl, (C6-Ci0)Aryl, (C7-C2o)Aralkyl oder (C7-C2o)Alkylaryl darstellen. Beispiele sind [NH4J+, [NH3CH3J+, [NH2(CH3)Z]+, [NH(CH3)3]\ [N(CH3M+, [NH2CH3C2Hs]+ oder [NH2CH3CeH5]+. In Frage kommen auch Alkylsulfonium- und Alkylsulfoxoniumsalze, wie (CrCO-Trialkylsulfonium- und (CrC4)-Trialkylsulfoxoniumsalze.The compounds of the formula (I) can form agrochemically suitable salts. Salt formation can in a known manner, for. Example, by the action of a base on such compounds of formula (I), which carry an acidic hydrogen atom, for example, in the case that R 1 contains an OH group or a sulfonamide group -NHSO 2 -. Salt formation can also be achieved by the action of a base on CH-acidic compounds, such as (substituted) propanedinitriles. Suitable bases are, for example, organic amines, such as trialkylamines, morpholine, piperidine or pyridine, and ammonia, ammonium, alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and potassium bicarbonate. These salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also salts with organic amines or ammonium salts, for example with ammonium ions of the formula NRR 'R "R"'] \ wherein R, R ', R "and R'" are each independently H or an organic radical, in particular (C-ι-C6) alkyl, (C 6 -C 0) aryl, (C 7 -C 2 o) aralkyl or (C 7 -C 2 o) alkylaryl represent. Examples are [NH 4 J + , [NH 3 CH 3 J + , [NH 2 (CH 3 ) Z] + , [NH (CH 3 ) 3 ] \ [N (CH 3 M + , [NH 2 CH 3 C 2 Hs] + or [NH 2 CH 3 CeH 5 ] + . Also suitable are alkylsulfonium and alkylsulfoxonium salts, such as (CrCO-trialkylsulfonium and (C 1 -C 4 ) -trialkylsulfoxonium salts.
Die Verbindungen der Formel (I) können durch Anlagerung einer geeigneten anorganischen oder organischen Säure, beispielsweise Mineralsäuren, wie beispielsweise HCl, HBr, H2SO4, H3PO4 oder HNO3, oder organische Säuren, z. B. Carbonsäuren, wie Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Milchsäure oder Salicylsäure, oder Sulfonsäuren, wie zum Beispiel p-Toluolsulfonsäure, an eine basische Gruppe, wie Amino, Alkylamino, Dialkylamino, Piperidino, Moφholino oder Pyridino, Salze bilden. Diese Salze enthalten dann die konjugierte Base der Säure als Anion. Geeignete Substituenten, die in deprotonierter Form, wie z.B. Sulfonsäuren, Carbonsäuren oder CH-acide Gruppen, wie Propandinitrile, vorliegen, können auch innere Salze mit ihrerseits protonierbaren Gruppen, wie Aminogruppen, bilden.The compounds of formula (I) may be prepared by addition of a suitable inorganic or organic acid, for example mineral acids such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, e.g. As carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid, or sulfonic acids, such as p-toluenesulfonic acid, to a basic group such as amino, alkylamino, dialkylamino, piperidino, Moφholino or pyridino, salts. These salts then contain the conjugate base of the acid as an anion. Suitable substituents which are present in deprotonated form, such as, for example, sulfonic acids, carboxylic acids or CH-acidic groups, such as propanedinitriles, can also form internal salts with groups which can themselves be protonated, such as amino groups.
Die Verbindungen der Formel (I) können N-Oxide bilden. Die N-Oxide können in bekannterweise z. B. durch Oxidation der jeweiligen Pyrimidine mit Peroxycarbonsäuren oder Wasserstoffperoxid in Lösungsmitteln wie Acetonitril, Dichlormethan, Chloroform, Aceton, DMF, Essigsäure, z. B. bei Temperaturen zwischen 0° und 1000C gebildet werden (siehe: S. von Angerer, Science of Synthesis 2003, 16, 548-550 und die jeweils darin zitierte Literatur).The compounds of formula (I) may form N-oxides. The N-oxides may be known in z. B. by oxidation of the respective pyrimidines with peroxycarboxylic acids or hydrogen peroxide in solvents such as acetonitrile, dichloromethane, chloroform, acetone, DMF, acetic acid, eg. B. at temperatures between 0 ° and 100 0 C are formed (see: S. von Angerer, Science of Synthesis 2003, 16, 548-550 and each cited therein literature).
Die Verbindungen der Formel (I) und deren N-Oxide und agrochemisch geeigneten Salze werden auch kurz als erfindungsgemäß verwendete oder erfindungsgemäße Verbindungen bezeichnet. Die vorstehend und weiter unten verwendeten Bezeichnungen sind dem Fachmann geläufig und haben insbesondere die im Folgenden erläuterten Bedeutungen:The compounds of the formula (I) and their N-oxides and agrochemically suitable salts are also referred to briefly as compounds used according to the invention or according to the invention. The terms used above and below are familiar to the person skilled in the art and in particular have the meanings explained below:
Ein anorganischer Rest ist ein Rest ohne Kohlenstoffatome, vorzugsweise Halogen, OH und dessen anorganische Salze, bei denen das H durch ein Kation, beispielsweise Alkalimetall- und Erdalkalimetallsalze ersetzt wird, -NH2 und dessen Ammoniumsalze mit (anorganischen) Säuren, beispielsweise Mineralsäuren, -N3 (Azid), -N2 +A" (Diazonium-Gruppe, wobei A" ein Anion darstellt), -NO, -NHOH, -NHNH2, -NO2, -ONO, -ONO2, -SH, -SOH (Sulfensäure-Gruppe), -S(O)OH (Sulfinsäure-Gruppe), -S(O)2OH (oder auch kurz SO3H, Sulfonsäure-Gruppe), -0-SO2H (Sulfit-Gruppe), -0-SO3H (Sulfat-Gruppe), -SO2NH2 (Sulfamoyl-Gruppe), -SO2NHOH (Hydroxysulfamoyl-Gruppe), -NHS(O)OH (Sulfinoamino-Gruppe), -NHS(O)2OH (Sulfoamino-Gruppe), -P(O)(OH)2 (Phosphonsäure-Gruppe),An inorganic radical is a radical without carbon atoms, preferably halogen, OH and its inorganic salts in which the H is replaced by a cation, for example alkali metal and alkaline earth metal salts, -NH 2 and its ammonium salts with (inorganic) acids, for example mineral acids, N 3 (azide), -N 2 + A " (diazonium group, wherein A " represents an anion), -NO, -NHOH, -NHNH 2 , -NO 2 , -ONO, -ONO 2 , -SH, - SOH (sulfenic acid group), -S (O) OH (sulfinic acid group), -S (O) 2 OH (or also short SO 3 H, sulfonic acid group), -O-SO 2 H (sulfite group) , -O-SO 3 H (sulfate group), -SO 2 NH 2 (sulfamoyl group), -SO 2 NHOH (hydroxysulfamoyl group), -NHS (O) OH (sulfinoamino group), -NHS (O ) 2 OH (sulfoamino group), -P (O) (OH) 2 (phosphonic acid group),
-0-P(OH)3 (Phosphat-Gruppe), -P(O)(NH2)2, -PO(OH)(NH2), -PS(OH)2, -PS(NH2)2 oder -PS(OH)(NH2), -B(OH)2 (Boronsäure-Gruppe) und die hydratisierten oder dehydratisierten Formen der Säuregruppen sowie deren (anorganischen) Salze; der Begriff "anorganischer Rest" umfasst auch den Wasserstoffrest (das Wasserstoffatom), wobei dieser in den Definitionen oft bereits Bestandteil des unsubstituierten Grundkörpers eines organischen Restes ist (Beispiel "unsubstituiertes Phenyl"); der Begriff "anorganischer Rest" umfasst hier vorzugsweise nicht Pseudohalogen- Gruppen wie CN, SCN, organische Metallkomplexe, Carbonat oder COOH, die wegen des Gehalts an C-Atomen den organischen Resten zugeordnet werden.-O-P (OH) 3 (phosphate group), -P (O) (NH 2 ) 2 , -PO (OH) (NH 2 ), -PS (OH) 2 , -PS (NH 2 ) 2 or -PS (OH) (NH 2 ), -B (OH) 2 (boronic acid group) and the hydrated or dehydrated forms of the acid groups and their (inorganic) salts; the term "inorganic radical" also includes the hydrogen radical (the hydrogen atom), which in the definitions often already part of the unsubstituted body of an organic radical is (example "unsubstituted phenyl"); The term "inorganic radical" here preferably does not include pseudohalogen groups such as CN, SCN, organic metal complexes, carbonate or COOH, which are assigned to the organic radicals because of the content of carbon atoms.
Die Bezeichnung "Halogen" oder „Halogenatom" bedeutet beispielsweise Fluor, Chlor, Brom oder lod.The term "halogen" or "halogen atom" means, for example, fluorine, chlorine, bromine or iodine.
Wird die Bezeichnung für einen Rest verwendet, dann bedeutet "Halogen" oder „Halogenatom" beispielsweise ein Fluor-, Chlor-, Brom- oder lodatom.When the term of a group is used, "halogen" or "halogen atom" means, for example, a fluorine, chlorine, bromine or iodine atom.
Alkyl bedeutet einen geradkettigen, verzweigten oder cyclischenAlkyl is straight-chain, branched or cyclic
Kohlenwasserstoffrest. Der Ausdruck "(Ci-C4)Alkyl" bedeutet beispielsweise eine Kurzschreibweise für Alkyl mit einem bis 4 Kohlenstoffatomen entsprechend der Bereichsangabe für C-Atome und umfasst z.B. die Reste Methyl, Ethyl, 1-Propyl, 2- Propyl, 1-Butyl, 2-Butyl, 2-Methylpropyl, tert-Butyl, Cyclopropyl und Cyclobutyl. Allgemeine Alkylreste mit einem größeren angegebenen Bereich von C-Atomen, z. B. "(CrCβJAlkyl", umfassen entsprechend auch gradkettige, verzweigte oder cyclische Alkylreste mit einer größeren Zahl von C-Atomen, d. h. gemäß Beispiel auch die Alkylreste mit 5 und 6 C-Atomen. Wenn nicht speziell angegeben, sind bei den Kohlenwasserstoffresten wie Alkyl-, Alkenyl- und Alkinylresten, auch in zusammengesetzten Resten, die niederenHydrocarbon radical. The term "(C 1 -C 4 ) alkyl" denotes, for example, a short notation for alkyl having one to 4 carbon atoms corresponding to the range given for C atoms and includes, for example, the radicals methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, cyclopropyl and cyclobutyl. General alkyl radicals having a larger specified range of carbon atoms, eg. Correspondingly, straight-chain, branched or cyclic alkyl radicals with a larger number of carbon atoms, ie, according to the example, also the alkyl radicals having 5 and 6 carbon atoms, are also included in the hydrocarbon radicals such as alkyl, for example "(C 1 -C 6) alkyl" -, alkenyl and alkynyl, even in assembled radicals, the lower
Kohlenstoffgerüste, z.B. mit 1 bis 6 C-Atomen bzw. bei ungesättigten Gruppen mit 2 bis 6 C-Atomen, bevorzugt. Alkylreste, auch in den zusammengesetzten Resten wie Alkoxy, Haloalkyl usw., bedeuten z.B. Methyl, Ethyl, Cyclo-, n- oder i-Propyl, Cyclo-, n-, i-, t- oder 2-Butyl, Pentyle, Hexyle, wie Cyclohexyl, n-Hexyl, i-Hexyl und 1 ,3-Dimethylbutyl, Heptyle, wie Cycloheptyl, n-Heptyl, 1 -Methylhexyl und 1 ,4-Dimethylpentyl. Bevorzugte cyclische Alkylreste weisen vorzugsweise 3-8 Ring-C-Atome auf, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Im Falle von gegebenenfalls substituierten cyclischen Alkylresten werden cyclische Systeme mit Substituenten umfasst, wobei auch Substituenten mit einer Doppelbindung am cyclischen Alkylrest, z. B. eine Alkylidengruppe wie Methyliden, umfasst sind.Carbon skeletons, for example having 1 to 6 carbon atoms or in unsaturated groups having 2 to 6 carbon atoms, are preferred. Alkyl radicals, including in the assembled radicals such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, cyclo, n- or i-propyl, cyclo, n-, i-, t- or 2-butyl, pentyls, hexyls, such as cyclohexyl, n-hexyl, i-hexyl and 1, 3-dimethylbutyl, heptyls such as cycloheptyl, n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl. Preferred cyclic alkyl radicals preferably have 3-8 ring C atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. In the case of optionally substituted cyclic alkyl radicals cyclic systems are included with substituents, wherein substituents having a double bond on the cyclic alkyl radical, for. As an alkylidene group such as methylidene, are included.
Im Falle von gegebenenfalls substituierten cyclischen Alkylresten werden auch mehrcyclische aliphatische Systeme umfaßt, wie Bicyclo[1.1.0]butan-1-yl, Bicyclo[1.1.0]butan-2-yl, Bicyclo[2.1.0]pentan-1-yl, Bicyclo[2.1.0]pentan-2-yl, Bicyclo[2.1.0]pentan-5-yl, Bicyclo[2.2.1]hept-2-yl (Norbornyl), Adamantan-1-yl und Adamantan-2-yl.In the case of optionally substituted cyclic alkyl radicals, polycyclic aliphatic systems are also included, such as bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentan-1-yl , Bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, bicyclo [2.2.1] hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2 yl.
Im Falle von gegebenenfalls substituierten cyclischen Alkylresten werden auch spirocyclische aliphatische Systeme umfaßt, wie beispielsweise Spiro[2.2]pent-1-yl, Spiro[2.3]hex-1-yl, Spiro[2.3]hex-4-yl, 3-Spiro[2.3]hex-5-yl.In the case of optionally substituted cyclic alkyl radicals, spirocyclic aliphatic systems are also included, such as spiro [2.2] pent-1-yl, spiro [2.3] hex-1-yl, spiro [2.3] hex-4-yl, 3-spiro [ 2.3] hex-5-yl.
Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten geradkettigen, verzweigten oder cyclischen Reste, wobei mindestens eine Doppelbindung bzw. Dreifachbindung enthalten ist. Bevorzugt sind Reste mit einer Doppelbindung bzw. mit einer Dreifachbindung. Alkenyl schließt auch geradkettige, verzweigte oder cyclische Kohlenwasserstoffreste mit mehr als einer Doppelbindung ein, wie 1 ,3-Butadienyl, 1 ,4-Pentadienyl oder Cyclohexadienyl, aber auch Allenyl- oder Kumulenyl-reste mit einer bzw. mehreren kumulierten Doppelbindungen, wie beispielsweise Allenyl (1 ,2-Propadienyl), 1 ,2-Butadienyl und 1 ,2,3-Pentatrienyl. Alkinyl schließt auch geradkettige, verzweigte oder cyclische Kohlenwasserstoffreste mit mehr als einer Dreifachbindung oder auch mit einer oder mehreren Dreifachbindungen und einer oder mehreren Doppelbindungen ein, wie beispielsweise 1 ,3-Butatrienyl bzw. 3-Penten-1-in-1-yl.Alkenyl and alkynyl radicals have the meaning of the possible unsaturated straight-chain, branched or cyclic radicals corresponding to the alkyl radicals, wherein at least one double bond or triple bond is contained. Preference is given to radicals having a double bond or having a triple bond. Alkenyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one double bond, such as 1, 3-butadienyl, 1, 4-pentadienyl or cyclohexadienyl, but also allenyl or cumulylene radicals having one or more cumulative double bonds, such as allenyl (1,2-propadienyl), 1,2-butadienyl and 1,2,3-pentatrienyl. Alkynyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one triple bond or else having one or more triple bonds and one or more double bonds, for example 1,3-butatrienyl or 3-penten-1-yn-1-yl.
Alkenyl bedeutet z.B. Vinyl, welches ggf. durch weitere Alkylreste substituiert sein kann, z.B. Prop-1-en-1-yl, But-1-en-1-yl; AIIyI, 1-Methyl-prop-2-en-1-yl, 2-Methyl-prop-2-en-1-yl, But-2-en-1-yl,Alkenyl means e.g. Vinyl, which may optionally be substituted by further alkyl radicals, e.g. Prop-1-en-1-yl, but-1-en-1-yl; Allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl,
1-Methyl-but-3-en-1-yl und 1-Methyl-but-2-en-1-yl, 2-Methylprop-1-en-1-yl, 1 -Methylprop-1 -en-1 -yl, 1 -Methylprop-2-en-1 -yl, 2-Methyl-prop-2-en-1 -yl, But-2-en-1-yl, But-3-en-1-yl, 1 -Methyl-but-3-en-1 -yl oder 1-Methyl-but-2-en-1-yl, Pentenyl, 2-Methylpentenyl oder Hexenyl.1-methylbut-3-en-1-yl and 1-methyl-but-2-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-1-ene-1 - yl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, But-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl or 1-methyl-but-2-en-1-yl, pentenyl, 2-methylpentenyl or hexenyl.
(C2-C6) -Alkinyl bedeutet beispielsweise Ethinyl, Propargyl, 1-Methyl-prop-2-in-1-yl, 2-Butinyl, 2-Pentinyl oder 2-Hexinyl, vorzugsweise Propargyl, But-2-in-1-yl, But-3-in-1 -yl oder 1 -Methyl-but-3-in-1 -yl.(C 2 -C 6 ) -alkynyl is, for example, ethinyl, propargyl, 1-methyl-prop-2-yn-1-yl, 2-butynyl, 2-pentynyl or 2-hexynyl, preferably propargyl, but-2-yn 1-yl, but-3-yn-1-yl or 1-methyl-but-3-yn-1-yl.
Cyclische Alkenylreste bedeuten ein carbocyclisches, nicht aromatisches, partiell ungesättigtes Ringsystem mit vorzugsweise 4-8 C-Atomen, z.B. 1-Cyclobutenyl, 2-Cyclobutenyl, 1-Cyclopentenyl, 2-Cyclopentenyl, 3-Cyclopentenyl, oder 1-Cyclohexenyl, 2-Cyclohexenyl, 3-Cyclohexenyl, 1 ,3-Cyclohexadienyl oder 1 ,4-Cyclohexadienyl, wobei auch Substituenten mit einer Doppelbindung am Cycloalkenylrest, z. B. eine Alkylidengruppe wie Methyliden, umfasst sind. Im Falle von gegebenenfalls substituiertem Cycloalkenyl gelten die Erläuterungen für substituierte cyclische Alkylreste entsprechend.Cyclic alkenyl radicals represent a carbocyclic, non-aromatic, partially unsaturated ring system preferably having 4-8 C atoms, e.g. 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1, 3-cyclohexadienyl or 1, 4-cyclohexadienyl, wherein also substituents with a Double bond on Cycloalkenylrest, z. As an alkylidene group such as methylidene, are included. In the case of optionally substituted cycloalkenyl, the explanations for substituted cyclic alkyl radicals apply correspondingly.
Alkyliden, z. B. auch in der Form (CrCiO)Alkyliden, bedeutet den Rest eines geradkettigen, verzweigten oder cyclischen Kohlenwasserstoffrests, der über eine Zweifachbindung gebunden ist. Als Bindungsstelle für Alkyliden kommen naturgemäß nur Positionen am Grundkörper in Frage, an denen zwei H-Atome durch die Doppelbindung ersetzt werden können; Reste sind z. B. =CH2, =CH-CH3, =C(CH3)-CH3, =C(CH3)-C2H5 oder =C(C2H5)-C2H5.Alkylidene, e.g. B. also in the form (CrCi O ) alkylidene, means the radical of a straight-chain, branched or cyclic hydrocarbon radical, which is bonded via a double bond. As a binding site for alkylidene naturally only positions on the body in question, in which two H atoms can be replaced by the double bond; Remains are z. B. = CH 2 , = CH-CH 3 , = C (CH 3 ) -CH 3 , = C (CH 3 ) -C 2 H 5 or = C (C 2 H 5 ) -C 2 H 5 .
Aryl bedeutet ein mono-, bi- oder polycyclisches aromatisches System mit vorzugsweise 6 bis 14, insbesondere 6 bis 10 Ring-C-Atomen, beispielsweise Phenyl, Naphthyl, Anthryl, Phenanthrenyl, und ähnliches, vorzugsweise Phenyl.Aryl is a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
Im Falle gegebenenfalls substituierten Aryls sind auch mehrcyclische Systeme, wie Tetrahydronaphtyl, Indenyl, Indanyl, Fluorenyl, Biphenylyl, umfasst, wobei die Bindungsstelle am aromatischen System ist. Von der Systematik her ist Aryl in der Regel auch von dem Begriff „gegebenenfalls substituiertes Phenyl" umfasst.In the case of optionally substituted aryl, more cyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, are included, the binding site being on the aromatic system. As a rule, aryl is also encompassed by the term "optionally substituted phenyl".
Mit der Definition „mit einem oder mehreren Resten substituiert ist" sind, wenn nicht anders definiert, unabhängig voneinander ein oder mehrere gleiche oder verschiedene Reste gemeint, wobei zwei oder mehrere Reste an einem Cyclus als Grundkörper einen oder mehrere Ringe bilden können.With the definition "substituted by one or more radicals" are, if not is defined differently, independently of one another, meaning one or more identical or different radicals, it being possible for two or more radicals to form one or more rings on one cycle as the main body.
Substituierte Reste, wie ein substituierter Alkyl-, Alkenyl-, Alkinyl-, Aryl-, Phenyl-, Benzyl-, Heterocyclyl- und Heteroarylrest, bedeuten beispielsweise einen vom unsubstituierten Grundkörper abgeleiteten substituierten Rest, wobei die Substituenten beispielsweise einen oder mehrere, vorzugsweise 1 , 2 oder 3 Reste aus der Gruppe Halogen, Alkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy oder eine der Carboxygruppe äquivalente Gruppe, Cyano, Isocyano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyl, Mono- und Dialkylaminocarbonyl, substituiertes Amino, wie Acylamino, Mono- und Dialkylamino, Trialkylsilyl und gegebenenfalls substituiertes cyclisches Alkyl, gegebenenfalls substituiertes Aryl, gegebenenfalls substituiertes Heterocyclyl, wobei jeder der letztgenannten cyclischen Gruppen auch über Heteroatome oder divalente funktionelle Gruppen wie bei den genannten Alkylresten gebunden sein kann, und Alkylsulfinyl, wobei beide Enantiomere der Alkylsulfonylgruppe umfasst sind, Alkylsulfonyl Alkylphosphinyl, Alkylphosphonyl und, im Falle cyclischer Reste (= "cyclischer Grundkörper"), auch Alkyl, Haloalkyl, Alkylthio-alkyl, Alkoxy-alkyl, gegebenfalls substituiertes Mono- und Dialkyl-aminoalkyl und Hydroxy-alkyl bedeuten; im Begriff "substituierte Reste" wie substituiertes Alkyl (z.B. gradkettiges, verzweigtes oder cyclisches Alkyl) etc. sind als Substituenten zusätzlich zu den genannten gesättigten kohlenwasserstoffhaltigen Resten entsprechende ungesättigte aliphatische und aromatische Reste, wie gegebenenfalls substituiertes Alkenyl, Alkinyl, Alkenyloxy, Alkinyloxy, Alkenylthio, Alkinylthio, Alkenyloxycarbonyl, Alkinyloxycarbonyl, Alkenylcarbonyl, Alkinylcarbonyl, Mono- undSubstituted radicals, such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 radicals selected from the group consisting of halogen, alkoxy, alkylthio, hydroxy, amino, nitro, carboxy or a carboxy group equivalent group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as Acylamino, mono- and dialkylamino, trialkylsilyl and optionally substituted cyclic alkyl, optionally substituted aryl, optionally substituted heterocyclyl, wherein each of the latter cyclic groups may also be bonded via heteroatoms or divalent functional groups as in said alkyl radicals, and alkylsulfinyl, both enantiomers the alkylsulfonyl group are included, Alkylsulfonyl, alkylphosphinyl, alkylphosphonyl and, in the case of cyclic radicals (= "cyclic parent"), also alkyl, haloalkyl, alkylthio-alkyl, alkoxy-alkyl, optionally substituted mono- and dialkylaminoalkyl and hydroxyalkyl; in the term "substituted radicals" such as substituted alkyl (eg straight-chain, branched or cyclic alkyl) etc. are substituents in addition to the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, Alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and
Dialkenylaminocarbonyl, Mono- und Dialkinylaminocarbonyl, Mono- und Dialkenylamino, Mono- und Dialkinylamino, Trialkenylsilyl, Trialkinylsilyl, Phenyl, Phenoxy etc. eingeschlossen. Im Falle von substituierten cyclischen Resten mit aliphatischen Anteilen im Ring werden auch cyclische Systeme mit solchen Substituenten umfaßt, die mit einer Doppelbindung am Ring gebunden sind, z. B. mit einer Alkylidengruppe wie Methyliden oder Ethyliden oder einer Oxogruppe, Iminogruppe oder substituierten Iminogruppe substituiert sind. Wenn zwei oder mehrere Reste einen oder mehrere Ringe bilden, so können diese carbocyclisch, heterocyclisch, gesättigt, teilgesättigt, ungesättigt, beispielsweise auch aromatisch und gegebenenfalls weiter substituiert sein. Die annellierten Ringe sind vorzugsweise 5- oder 6-Ringe, besonders bevorzugt sind benzokondensierte Cyclen.Dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and dialkenylamino, mono- and dialkynylamino, trialkenylsilyl, trialkynylsilyl, phenyl, phenoxy, etc. included. In the case of substituted cyclic radicals having aliphatic moieties in the ring, cyclic systems are also included having such substituents attached to the ring by a double bond, e.g. B. substituted with an alkylidene group such as methylidene or ethylidene or an oxo group, imino group or substituted imino group. If two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and optionally further substituted. The fused rings are preferably 5- or 6-membered rings, particularly preferred are benzo-fused rings.
Die beispielhaft genannten Substituenten ("erste Substituentenebene") können, sofern sie kohlenwasserstoffhaltige Anteile enthalten, dort gegebenenfalls weiter substituiert sein ("zweite Substitutentenebene"), beispielsweise durch einen der Substituenten, wie er für die erste Substituentenebene definiert ist. Entsprechende weitere Substituentenebenen sind möglich. Vorzugsweise werden vom Begriff "substituierter Rest" nur ein oder zwei Substitutentenebenen umfasst.The exemplified substituents ("first substituent level"), if they contain hydrocarbon-containing moieties, may optionally be further substituted there ("second substituent plane"), for example by one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. Preferably, the term "substituted radical" includes only one or two substituent levels.
Bevorzugte Substituenten für die Substituentenebenen sind beispielsweise Amino, Hydroxy, Halogen, Nitro, Cyano, Isocyano, Mercapto, Isothiocyanato, Carboxy, Carbonamid, SF5, Aminosulfonyl, Alkyl, Alkenyl, Alkinyl, Monoalkyl-amino, Dialkyl-amino, N-Alkanoyl-amino, Alkoxy, Alkenyloxy, Alkinyloxy, Alkoxy-carbonyl, Alkenyloxy-carbonyl, Alkinyloxy-carbonyl, Aryloxycarbonyl, Alkanoyl, Alkenyl- carbonyl, Alkinyl-carbonyl, Aryl-carbonyl, Alkylthio, Alkenylthio, Alkinylthio,Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF 5 , aminosulfonyl, alkyl, alkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkanoyl- amino, alkoxy, alkenyloxy, alkynyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, alkenylthio, alkynylthio,
Alkylsulfenyl, Alkylsulfinyl, wobei beide Enantiomere der Alkylsulfinylgruppe umfasst sind, Alkylsulfonyl, Monoalkyl-aminosulfonyl, Dialkyl-aminosulfonyl, Alkylphosphinyl, Alkylphosphonyl, wobei für Alkylphosphinyl bzw. Alkylphosphonyl beide Enantiomere umfasst sind, N-Alkyl-aminocarbonyl, N,N-Dialkyl-aminocarbonyl, N-Alkanoyl-amino- carbonyl, N-Alkanoyl-N-alkyl-aminocarbonyl, Aryl, Aryloxy, Benzyl, Benzyloxy, Benzylthio, Arylthio, Arylamino, Benzylamino, Heterocyclyl und Trialkylsilyl.Alkylsulfenyl, alkylsulfinyl, wherein both enantiomers of the alkylsulfinyl group are included, alkylsulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylphosphinyl, alkylphosphonyl, wherein for alkylphosphinyl or alkylphosphonyl both enantiomers are included, N-alkyl-aminocarbonyl, N, N-dialkylaminocarbonyl , N-alkanoyl-amino-carbonyl, N-alkanoyl-N-alkyl-aminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclyl and trialkylsilyl.
Substituenten, die aus mehreren Substituentenebenen zusammengesetzt sind, sind bevorzugt beispielsweise Alkoxyalkyl, wie Monoalkoxyalkyl oder Dialkoxyalkyl, Alkylthioalkyl, Alkylthioalkoxy, Alkoxyalkoxy, wie Monoalkoxyalkoxy oderSubstituents composed of plural substituent levels are preferably, for example, alkoxyalkyl such as monoalkoxyalkyl or dialkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy such as monoalkoxyalkoxy or
Dialkoxyalkoxy, Benzyl, Phenethyl, Benzyloxy, Haloalkyl, Haloalkoxy, Haloalkylthio, Haloalkanoyl, Haloalkylcarbonyl, Haloalkoxycarbonyl, Haloalkoxyalkoxy, Haloalkoxyalkylthio, Haloalkoxyalkanoyl, Haloalkoxyalkyl, Alkanoylalkyl, Haloalkanoylalkyl, Alkanoyloxyalkyl.Dialkoxyalkoxy, benzyl, phenethyl, benzyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, Haloalkoxyalkylthio, haloalkoxyalkanoyl, haloalkoxyalkyl, alkanoylalkyl, haloalkanoylalkyl, alkanoyloxyalkyl.
Bei Resten mit C-Atomen sind solche mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, insbesondere 1 oder 2 C-Atomen bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, (Ci-C4)Alkyl, vorzugsweise Methyl oder Ethyl, (Ci-C4)Haloalkyl, vorzugsweise Trifluormethyl, (CrC4)AIkOXy, vorzugsweise Methoxy oder Ethoxy, (CrC4)Haloalkoxy, Nitro und Cyano. Besonders bevorzugt sind dabei die Substituenten Methyl, Methoxy, Fluor und Chlor.For radicals with carbon atoms, preference is given to those having 1 to 6 C atoms, preferably 1 to 4 C atoms, in particular 1 or 2 C atoms. As a rule, preferred substituents are selected from the group halogen, for example fluorine and chlorine, (Ci-C 4) alkyl, preferably methyl or ethyl, (Ci-C4) haloalkyl, preferably trifluoromethyl, (CrC 4) -alkoxy, preferably methoxy or ethoxy , (CrC 4 ) haloalkoxy, nitro and cyano. Particularly preferred are the substituents methyl, methoxy, fluorine and chlorine.
Substituiertes Amino wie mono- oder disubstituiertes Amino bedeutet einen Rest aus der Gruppe der substituierten Aminoreste, welche beispielsweise durch einen bzw. zwei gleiche oder verschiedene Reste aus der Gruppe Alkyl, Hydroxy, Amino, Alkoxy, Acyl und Aryl N-substituiert sind; vorzugsweise Mono- und Dialkyl-amino, Mono- und Diarylamino, wie gegebenenfalls substituierte Aniline, Acylamino, N1N- diacylamino, N-Alkyl-N-arylamino, N-Alkyl-N-acylamino sowie gesättigte N-Heterocyclen; dabei sind Alkylreste mit 1 bis 4 C-Atomen bevorzugt; Aryl ist dabei vorzugsweise Phenyl oder substituiertes Phenyl; für Acyl gilt dabei die weiter unten genannte Definition, vorzugsweise (d-C4)Alkanoyl. Entsprechenes gilt für substituiertes Hydroxylamino oder Hydrazino.Substituted amino such as mono- or disubstituted amino means a radical from the group of substituted amino radicals which are N-substituted, for example by one or two identical or different radicals from the group alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably mono- and dialkyl-amino, mono- and diarylamino, such as optionally substituted aniline, acylamino, N 1 N- diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; while alkyl radicals having 1 to 4 carbon atoms are preferred; Aryl is preferably phenyl or substituted phenyl; for acyl, the definition below applies, preferably (dC 4 ) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
Substituiertes Amino schließt auch quartäre Ammoniumverbindungen (Salze) mit vier organischen Substituenten am Stickstoffatom ein.Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.
Eine der Carboxygruppe äquivalente Gruppe bedeutet beispielsweise ein Alkylester, Arylester, O-Alkylthioester, S-Alkyldithioester, S-Alkylthioester, Carboximidester, Carboximidthioester; 5,6-Dihydro-1 ,2,4-dioxazin-3-yl; 5,6-Dihydro-1 ,2,4-oxathiazin-3- yl, Trialkylorthoester, Dialkoxyalkylaminoester, Dialkylaminoalkoxyester, Trialkylaminoester, Amidine, Dialkoxyketenacetale oder Dialkyldithioketenacetale.For example, a group equivalent to carboxy group means an alkyl ester, aryl ester, O-alkyl thioester, S-alkyl dithioester, S-alkyl thioester, carboximide ester, carboximide thioester; 5,6-dihydro-1,2,4-dioxazin-3-yl; 5,6-dihydro-1,2,4-oxathiazin-3-yl, trialkylorthoesters, dialkoxyalkylaminoesters, dialkylaminoalkoxyesters, trialkylaminoesters, amidines, dialkoxyketene acetals or dialkyldithioketene acetals.
Gegebenenfalls substituiertes Phenyl ist vorzugsweise Phenyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach durch gleiche oder verschiedene Reste aus der Gruppe Halogen, (C-ι-C4)Alkyl, (CrC4)Alkoxy, (Ci -C4)AIkOXy-(C1 -C4)alkoxy, (CrC4)Alkoxy-(C1-C4)alkyl, (CrC4)Halogenalkyl, (CrC4)Halogenalkoxy, (CrC4)Alkylthio, (CrC4)Halogenalkylthio, Cyano, Isocyano und Nitro substituiert ist, z.B. o-, m- und p-Tolyl, Dimethylphenyle, 2-, 3- und 4-Chlorphenyl, 2-, 3- und 4-Fluorphenyl, 2-, 3- und 4-Trifluormethyl- und -Trichlormethylphenyl, 2,4-, 3,5-, 2,5- und 2,3-Dichlorphenyl, o-, m- und p-Methoxyphenyl.Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times by the same or different radicals from the group halogen, (C-ι-C 4) alkyl, (CrC 4) alkoxy, (Ci -C 4) AIkOXy- (C 1 -C 4) alkoxy, (CrC 4) alkoxy (C 1 - C4) alkyl, (C r C 4) haloalkyl, (CrC 4) haloalkoxy, (CrC 4) alkylthio, (CrC 4) haloalkylthio, cyano, isocyano and nitro, for example o-, m- and p-tolyl, Dimethylphenyle , 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and -Trichlormethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
Gegebenenfalls substituiertes Heterocyclyl ist vorzugsweise Heterocyclyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach durch gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, (CrC4)Alkyl, (CrC4)AIkOXy, (CrC4)Alkoxy-(CrC4)alkoxy, (CrC4)Alkoxy-(Ci-C4)alkyl, (CrC4)Halogenalkyl, (C-ι-C4)Halogenalkoxy, Nitro und Oxo substituiert ist, insbesondere ein- oder mehrfach durch Reste aus der Gruppe Halogen, (CrC4)Alkyl, (Ci -C4)AI koxy, (CrC4)Halogenalkyl und Oxo, ganz besonders durch einen oder zwei (Ci-C4)Alkylreste substituiert ist.Optionally substituted heterocyclyl is preferably heterocyclyl is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group halogen, cyano, (C r C4) alkyl, (CrC 4) -alkoxy, (CrC 4) alkoxy - (C r C 4) alkoxy, (CrC 4) alkoxy (Ci-C 4) alkyl, (CrC 4) haloalkyl, (C-ι-C 4) haloalkoxy, nitro and oxo, in particular one or more times by radicals from the group halogen, (CrC 4) alkyl, (Ci -C 4) AI koxy, (CrC 4) haloalkyl and oxo, particularly by one or two (Ci-C4) alkyl substituted.
Haloalkyl, -alkenyl und -alkinyl bedeuten durch gleiche oder verschiedene Halogenatome, teilweise oder vollständig substituiertes Alkyl, Alkenyl bzw. Alkinyl, z.B. Monohaloalkyl (= Monohalogenalkyl) wie CH2CH2CI, CH2CH2F, CHCICH3,Haloalkyl, -alkenyl and -alkinyl denote by identical or different halogen atoms, partially or completely substituted alkyl, alkenyl or alkynyl, for example monohaloalkyl (= monohaloalkyl), such as CH 2 CH 2 Cl, CH 2 CH 2 F, CHCICH 3 ,
CHFCH3, CH2CI, CH2F; Perhaloalkyl wie CCI3 oder CF3 oder CF2CF3; Polyhaloalkyl wie CHF2, CH2F, CH2CHFCI, CHCI2, CF2CF2H, CH2CF3; Haloalkoxy ist z.B. OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 und OCH2CH2CI; Entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierten Reste.CHFCH 3 , CH 2 Cl, CH 2 F; Perhaloalkyl such as CCI 3 or CF 3 or CF 2 CF 3 ; Polyhaloalkyl such as CHF 2 , CH 2 F, CH 2 CHFCl, CHCl 2 , CF 2 CF 2 H, CH 2 CF 3 ; Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl; The same applies to haloalkenyl and other halogen-substituted radicals.
Ein organischer Säurerest bedeutet einen Rest einer Oxosäure oder Thiosäure der allgemeinen FormelAn organic acid residue means a residue of an oxo acid or thioacid of the general formula
R* E(=Q)P(OH) (QR')„R * E (= Q) P (OH) (QR ' ) "
wobeiin which
R ein organischer Rest, E ein Atom aus der Gruppe C, S, P,R is an organic residue, E is an atom from the group C, S, P,
Q unabhängig voneinander ein Atom oder ein Molekülfragment aus der Gruppe O,Q independently of one another an atom or a molecule fragment from the group O,
S, NR' undS, NR ' and
R' unabhängig voneinander ein Wasserstoffatom, Alkyl, Haloalkyl, Alkoxyalkyl oder gegebenenfalls Aryl bedeutet. k, p sind natürliche Zahlen, /c = 1 , 2; p = 0 - 2; n ist eine natürliche Zahl oder Null.R 'is independently a hydrogen atom, alkyl, haloalkyl, alkoxyalkyl or optionally aryl. k, p are natural numbers, / c = 1, 2; p = 0-2; n is a natural number or zero.
Der organische Säurerest entsteht formal durch Abtrennen einer Hydroxygruppe an der Säurefunktion, wobei der organische Rest R in der Säure auch über ein oder mehrere Heteroatome mit der Säurefunktion verbunden sein kann:The organic acid radical is formally formed by separating a hydroxy group on the acid function, wherein the organic radical R in the acid can also be connected via one or more heteroatoms with the acid function:
Für Oxosäuren des Kohlenstoffs ist dies im IUPAC Compendium of ChemicalFor oxo acids of carbon, this is in the IUPAC Compendium of Chemical
Terminology (1997) beschrieben.Terminology (1997).
Beispiele für organische Säurereste, die von den Oxosäuren bzw. Thiosäuren desExamples of organic acid residues derived from the oxo acids or thioacids of the
Schwefels abgeleitet sind (E = S), sind S(O)OCH3, SO2OH1 SO2OCH3 oder SO2NHRSulfur are derived (E = S), S (O) OCH 3 , SO 2 OH 1 SO 2 OCH 3 or SO 2 NHR
(N-substituierte Sulfonamidsäuren).(N-substituted sulfonamide acids).
Im Falle von k = 1 sind auch Alkylsulfonyl- und Alkylsulfinyl-Reste, wie z.B. (H3C)S(O)2, (F3C)S(O)2, P-ToIyIS(O)2, (H3C)S(O)(NH-Ii-C4H9), (C6H5)S(S)(O) oderIn the case of k = 1 are also alkylsulfonyl and alkylsulfinyl radicals, such as (H 3 C) S (O) 2 , (F 3 C) S (O) 2 , P-ToIyIS (O) 2 , (H 3 C) S (O) (NH-Ii-C 4 H 9 ), (C 6 H 5 ) S (S) (O) or
(C6H5)S(O) mit umfasst.(C 6 H 5 ) S (O).
Beispiele für organische Säurereste, die von den Oxosäuren bzw. Thiosäuren desExamples of organic acid residues derived from the oxo acids or thioacids of the
Phosphors abgeleitet sind (E = P), sind von der Phosphinsäure und derPhosphors are derived (E = P), are from the phosphinic acid and the
Phosphonsäure abgeleitete Reste, wobei diese Reste weiter verestert sein können, z.B. -PO(OCH3)2, (C2H5O)P(O)OH, (C2H5O)P(O)(SC6H5), (H3CO)P(O)NH(C6H5) oderPhosphonic acid derived radicals, which radicals may be further esterified, for example -PO (OCH 3 ) 2 , (C 2 H 5 O) P (O) OH, (C 2 H 5 O) P (O) (SC 6 H 5 ), (H 3 CO) P (O) NH (C 6 H 5 ) or
-PO(NMe2)2.-PO (NMe 2 ) 2 .
Im Falle von k = 1 sind auch Alkylphosphinyl- und Alkylphosphonyl-Reste, wie z.B.In the case of k = 1, alkylphosphinyl and alkylphosphonyl radicals, e.g.
(H3C)2 P(O), (C6Hg)2P(O), (H3C)(C6H5)P(O); (H3C)P(O)OCH3, (H5C2)P(O)(OC2H5),(H 3 C) 2 P (O), (C 6 Hg) 2 P (O), (H 3 C) (C 6 H 5 ) P (O); (H 3 C) P (O) OCH 3 , (H 5 C 2 ) P (O) (OC 2 H 5 ),
(C6H5)P(O)(OC2H5), (C2H5)P(O)(SC6H5), (H3C)P(O)NH(C6H5), (H3C)P(S)(NH-J-C3H7), (C6H5)P(S)(OC2H5) oder (C6H5)P(S)(SC2H5) mit umfasst.(C 6 H 5 ) P (O) (OC 2 H 5 ), (C 2 H 5 ) P (O) (SC 6 H 5 ), (H 3 C) P (O) NH (C 6 H 5 ) , (H 3 C) P (S) (NH-JC 3 H 7 ), (C 6 H 5 ) P (S) (OC 2 H 5 ) or (C 6 H 5 ) P (S) (SC 2 H 5 ).
Organische Säurereste, die von den Oxosäuren des Kohlenstoffs abgeleitet sind (E = C1 Q = O), werden im engeren Sinne auch mit dem Begriff „Acyl" bezeichnet.Organic acid radicals derived from the oxo acids of carbon (E = C 1 Q = O) are also referred to in the narrower sense by the term "acyl".
Beispiele für Acyl sind der Rest -CO-R einer Carbonsäure HO-CO-R und Reste davon abgeleiteter Säuren oder der Rest von Kohlensäuremonoestern oder N-substituierter Carbaminsäuren sowie Carbonate und deren Ester.Examples of acyl are the radical -CO-R of a carboxylic acid HO-CO-R and radicals derived therefrom or the radical of carbonic acid monoesters or N-substituted carbamic acids and carbonates and their esters.
Acyl bedeutet beispielsweise Formyl, Oxalyl(ester), Alkylcarbonyl wieAcyl, for example, formyl, oxalyl (ester), alkylcarbonyl as
[(CrC4)Alkyl]-carbonyl, Haloalkylcarbonyl, Phenylcarbonyl, Alkyloxycarbonyl, speziell tert.-Butyloxycarbonyl, Phenyloxycarbonyl, Benzyloxycarbonyl, Fluorenyloxycarbonyl, N-Alkyl-1-iminoalkyl, N-Alkyl- und N.N-Dialkylcarbamoyl. Dabei können die Reste jeweils im Alkyl- oder Phenylteil noch weiter substituiert sein, beispielsweise im Alkylteil durch ein oder mehrere Reste aus der Gruppe Halogen, Cyano, Alkoxy, Phenyl und Phenoxy; Beispiele für Substituenten im Phenylteil sind die bereits weiter oben allgemein für substituiertes Phenyl erwähnten Substituenten.[(C 1 -C 4 ) alkyl] carbonyl, haloalkylcarbonyl, phenylcarbonyl, alkyloxycarbonyl, especially tert-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, fluorenyloxycarbonyl, N-alkyl-1-iminoalkyl, N-alkyl and NN -dialkylcarbamoyl. The radicals may each be further substituted in the alkyl or phenyl part, for example in the alkyl part by one or more radicals from the group halogen, cyano, alkoxy, phenyl and phenoxy; Examples of substituents in the phenyl moiety are the substituents already mentioned above generally for substituted phenyl.
Acyl bedeutet vorzugsweise einen Acylrest im engeren Sinne, d.h. einen Rest einer organischen Säure, bei der die Säuregruppe direkt mit dem C-Atom eines organischen Restes verbunden ist, beispielsweise Alkanoyl, wie Formyl und Acetyl, Aroyl wie Phenylcarbonyl, und andere Reste von gesättigten oder ungesättigten organischen Säuren.Acyl is preferably an acyl radical in the strict sense, i. a residue of an organic acid in which the acid group is bonded directly to the carbon atom of an organic group, for example, alkanoyl such as formyl and acetyl, aroyl such as phenylcarbonyl, and other groups of saturated or unsaturated organic acids.
"Aroyl" bedeutet einen wie vorstehend definierter Arylrest, der über eine Carbonyl- Gruppe gebunden ist, z.B. die Benzoyl-Gruppe."Aroyl" means an aryl radical as defined above bonded through a carbonyl group, e.g. the benzoyl group.
Wenn ein allgemeiner Rest mit "Wasserstoff' definiert ist, bedeutet dies ein Wasserstoffatom.When a general radical is defined as 'hydrogen', it means a hydrogen atom.
Mit "yl-Position" eines Restes ist dessen Bindungstelle bezeichnet. Gegenstand der vorliegenden Erfindung sind auch Methoden zur Herstellung der erfindungsgemäßen Verbindungen. Die erfindungsgemäßen Verbindungen können alternativ durch verschiedene Verfahren dargestellt werden.With "yl position" of a radical whose binding site is designated. The present invention also provides methods for the preparation of the compounds according to the invention. The compounds of the invention may alternatively be prepared by various methods.
In den nachfolgenden Verfahren werden partiell Lösemittel verwendet. In diesem Zusammenhang bezeichnen „inerte Lösemittel" jeweils Lösemittel, die unter den jeweiligen Reaktionsbedingungen inert sind, jedoch nicht unter beliebigen Reaktionsbedingen inert sein müssen.In the following procedures partially solvents are used. In this context, "inert solvents" in each case solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
Verbindungen der Formel (I) können z. B. durch Reaktion der entsprechenden Halogenverbindungen (II) mit dem jeweiligen Amin der Formel (IM) hergestellt werden, optional unter Verwendung einer organischen oder anorganischen Base (z. B. Triethylamin, Pyridin, Kaliumcarbonat, Natriumcarbonat). Die Reaktion kann in verschiedenen Lösungsmitteln wie Methanol, Ethanol, Dioxan, THF, Dichlormethan, DMSO1 DMF und Wasser durchgeführt werden. Die Reaktionstemperaturen liegen je nach verwendetem Amin im Allgemeinen zwischen 200C und 1800C.Compounds of formula (I) may, for. Example by reaction of the corresponding halogen compounds (II) with the respective amine of formula (IM), optionally using an organic or inorganic base (eg., Triethylamine, pyridine, potassium carbonate, sodium carbonate). The reaction can be carried out in various solvents such as methanol, ethanol, dioxane, THF, dichloromethane, DMSO 1 DMF and water. The reaction temperatures are generally between 20 ° C. and 180 ° C., depending on the amine used.
( H ) ( IM ) ( I )(H) (IM) (I)
Verbindungen der Formel (M) können z. B. durch Reaktion der entsprechenden 4,6- Dihalogenverbindungen (IV) mit dem jeweiligen Alkalisalz des Malondinitrils erhalten werden. Die jeweiligen Salze können z. B. in situ durch Behandlung von Malondinitril mit verschiedenen Basen wie z.B. n-Butyllithium, Lithiumdiisopropylamid, Natriumhydrid oder Kaliumcarbonat bei Temperaturen zwischen -800C und 800C generiert werden. Nach Zugabe der 4,6-Dihalogenpyrimidine (IV) wird die Reaktion in einem Temperaturbereich zwischen O0C und 1000C durchgeführt, bevorzugt in aprotischen Lösungsmitteln wie THF, DMSO, DMF oder Dioxan. Compounds of formula (M) may, for. B. by reaction of the corresponding 4,6-dihalogen compounds (IV) with the respective alkali metal salt of the malononitrile. The respective salts may, for. B. in situ by treatment of malononitrile with various bases such as n-butyl lithium, lithium diisopropylamide, sodium hydride or potassium carbonate at temperatures between -80 0 C and 80 0 C are generated. After addition of the 4,6-Dihalogenpyrimidine (IV), the reaction is carried out in a temperature range between 0 0 C and 100 0 C, preferably in aprotic solvents such as THF, DMSO, DMF or dioxane.
( IV ) ( II )(IV) (II)
Die Herstellung von Verbindungen der Formel (IV) erfolgt durch allgemein bekannte Methoden: K. Findeisen, K. Wagner, Synthesis 1978, 40-42; H. Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961 , 26, 1874-1877; H. Gershon, R. Braun, A. Scala, R. Rodin, J. Med. Chem. 1964, 7, 808-811 ; D. T. Hurst, Heterocycles 1984, 22, 79-84; L. Provins et al., Bioorg. Med. Chem. Lett. 2006, 16, 1834-1839; T. Sakamoto, Y. Kondo, R. Watanabe, H. Yamanaka, Chem. Pharm. Bull. 1986, 34, 2719-2724; S. von Angerer, Science of Synthesis 2003, 16, 379-572 und die jeweils darin zitierte Literatur. In den Formeln (II), (III) und (IV) haben die Reste R1, R2, R3 und R4 die gleiche Bedeutung wie in Formel (I), HaI in Formel (II) und (IV) bedeutet ein Halogenatom, wobei bei mehreren HaI in Formel (IV) jeweils unterschiedliche Halogene vorliegen können.The preparation of compounds of formula (IV) is carried out by well-known methods: K. Findeisen, K. Wagner, Synthesis 1978, 40-42; Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961, 26, 1874-1877; Gershon, R. Braun, A. Scala, R. Rodin, J. Med. Chem. 1964, 7, 808-811; DT Hurst, Heterocycles 1984, 22, 79-84; L. Provins et al., Bioorg. Med. Chem. Lett. 2006, 16, 1834-1839; T. Sakamoto, Y. Kondo, R. Watanabe, H. Yamanaka, Chem. Pharm. Bull. 1986, 34, 2719-2724; S. von Angerer, Science of Synthesis 2003, 16, 379-572 and the literature cited therein. In the formulas (II), (III) and (IV), the radicals R 1 , R 2 , R 3 and R 4 have the same meaning as in formula (I), Hal in the formula (II) and (IV) represents a Halogen atom, where in each case different halogens may be present in several Hal in formula (IV).
Kollektionen aus erfindungsgemäßen Verbindungen, die nach den oben genannten Reaktionen synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley 1999, auf den Seiten 1 bis 34 beschrieben ist.Collections of compounds of the present invention which can be synthesized following the above reactions can also be prepared in a parallelized manner, which can be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, beispielsweise Calypso- Reaktionsblöcke (Calypso reaction blocks) der Firma Barnstead International, Dubuque, Iowa 52004-0797, USA oder Reaktionsstationen (reaction stations) der Firma Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England oder MultiPROBE Automated Workstations der Firma Perkin Elmar, Waltham, Massachusetts 02451 , USA. Für die parallelisierte Aufreinigung von erfindungsgemäßen Verbindungen beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.For parallelized reaction performance and work-up, a number of commercially available devices may be used, for example Calypso reaction blocks (Calypso reaction blocks) from Barnstead International, Dubuque, Iowa 52004-0797, USA or Reaction Stations of the Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations of Perkin Elmar, Waltham, Massachusetts 02451, USA. For the parallelized purification of compounds according to the invention or of intermediates obtained during the preparation, among other things, chromatography equipment is available, for example the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständig integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Caliper, Hopkinton, MA 01748, USA bezogen werden.The listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed. This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
Die Durchführung einzelner oder mehrerer Syntheseschritte kann durch den Einsatz von Polymer-supported reagents/Scavanger-Harze unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in ChemFiles, Vol. 4, No. 1 , Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).The implementation of single or multiple synthetic steps can be supported by the use of polymer-supported reagents / Scavanger resins. A number of experimental protocols are described in the literature, for example in ChemFiles, Vol. 1, Polymer-Supported Scavengers and Reagents for Solution Phase Synthesis (Sigma-Aldrich).
Neben den hier beschriebenen Methoden kann die Herstellung von erfindungsgemäßen Verbindungen vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende Vorgehensweise angepassten Synthese an ein Syntheseharz gebunden. Festphasen- unterstützte Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998 und Combinatorial Chemistry - Synthesis, Analysis, ScreeningIn addition to the methods described here, the preparation of compounds according to the invention can be carried out completely or partially by methods supported by solid phases. For this purpose, individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin. Solid phase assisted synthetic methods are well described in the literature, e.g. Barry A. Bunin in "The Combinatorial Index", Academic Press, 1998, and Combinatorial Chemistry - Synthesis, Analysis, Screening
(Herausgeber Günther Jung), Verlag Wiley, 1999. Die Verwendung von Festphasen- unterstützten Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Die Reaktionen können beispielsweise mittels IRORI-Technologie in Mikroreaktoren (microreactors) der Firma Nexus Biosystems, 12140 Community Road, Poway, CA32064, USA durchgeführt werden.(Published by Günther Jung), published by Wiley, 1999. The use of solid-phase assisted synthetic methods allows a number of literature-known Logs that can be executed manually or automatically. The reactions can be carried out, for example, by means of IRORI technology in microreactors (microreactors) from Nexus Biosystems, 12140 Community Road, Poway, CA32064, USA.
Sowohl an fester als auch in flüssiger Phase kann die Durchführung einzelner oder mehrerer Syntheseschritte durch den Einsatz der Mikrowellen-Technologie unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in Microwaves in Organic and Medicinal Chemistry (Herausgeber C. O. Kappe und a. Stadler), Verlag Wiley, 2005.Both solid and liquid phases can be supported by the implementation of single or multiple synthetic steps through the use of microwave technology. A number of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (publishers C. O. Kappe and A. Stadler), Verlag Wiley, 2005.
Die Herstellung gemäß der hier beschriebenen Verfahren liefert erfindungsgemäße Verbindungen in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei erfindungsgemäße Verbindungen enthalten.The preparation according to the methods described herein provides compounds of the invention in the form of substance collections called libraries. The present invention also provides libraries containing at least two compounds of the invention.
Die erfindungsgemäßen Verbindungen weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler annueller Schadpflanzen auf. Auch schwer bekämpfbare perennierende Schadpflanzen, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfasst.The compounds according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial harmful plants, which expel from rhizomes, rhizomes or other permanent organs are well detected by the active ingredients.
Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, vorzugsweise in Pflanzenkulturen, worin eine oder mehrere erfindungsgemäße Verbindung(en) auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle Unkräuter oder unerwünschte Kulturpflanzen), das Saatgut (z.B. Körner, Samen oder vegetative Vermehrungsorgane wie Knollen oder Sprossteile mit Knospen) oder die Fläche, auf der die Pflanzen wachsen (z.B. die Anbaufläche), ausgebracht werden. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat- (ggf. auch durch Einarbeitung in den Boden), Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im Einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.The present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied. The compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process. In particular, some are exemplary Representatives of the monocotyledonous and dicotyledonous weed flora called, which can be controlled by the compounds of the invention, without that by naming a restriction to certain species is to take place.
Monokotyle Schadpflanzen der Gattungen: Aegilops, Agropyron, Agrostis,Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis,
Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ishaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Dikotyle Schadpflanzen der Gattungen: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis Galinsoga Galium Hibiscus Ipomoea Kochia Lamium Lepidium Lindernia Matricaria Mentha Mercurialis Mullugo Myosotis Papaver Pharbitis Plantago Polygonum Portulaca Ranunculus Raphanus Rorippa Rotala Rumex , Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.If the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt nach der Behandlung Wachstumsstop ein und die Schadpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so dass auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird. Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Schadpflanzen aufweisen, werden Kuiturpfianzen wirtschaftlich bedeutender Kulturen wie dikotyler Kulturen, z.B. der Gattungen Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus,When the active ingredients are applied to the green parts of the plants postemergence, growth stops after the treatment and the harmful plants remain in the growth stage existing at the time of application or die completely after a certain time, so that a weed competition harmful to the crop plants takes place very early and sustainably eliminated. Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous harmful plants, cultivated plants of economically important crops, such as dicotyledonous crops, for example of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus,
Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, oder monokotyler Kulturen z.B. der Gattungen Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, insbesondere Zea und Triticum, abhängig von der Struktur der jeweiligen erfindungsgemäßen Verbindung und deren Aufwandmenge nur unwesentlich oder gar nicht geschädigt. Die erfindungsgemäßen Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in Pflanzenkulturen wie landwirtschaftlichen Nutzpflanzungen oder Zierpflanzungen.Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia or monocotyledonous cultures e.g. the genera Allium, Pineapple, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of the respective compound of the invention and their application rate only insignificantly or not at all damaged , For these reasons, the compounds according to the invention are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornamental plantings.
Darüber hinaus weisen die erfindungsgemäßen Verbindungen (abhängig von ihrer jeweiligen Struktur und der ausgebrachten Aufwandmenge) hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Des Weiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da beispielsweise die Lagerbildung hierdurch verringert oder völlig verhindert werden kann.In addition, the compounds according to the invention (depending on their respective structure and the applied application rate) have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, such as be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die erfindungsgemäßen Verbindungen auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z.B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt. Weitere besondere Eigenschaften können in einer Toleranz oder Resistenz gegen abiotische Stressoren z.B. Hitze, Kälte, Trockenheit, Salz und ultraviolette Strahlung liegen.On account of their herbicidal and plant growth-regulating properties, the compounds according to the invention can also be employed for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually distinguished by particular advantageous properties, for example by Resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known. Other special properties may include tolerance or resistance to abiotic stressors such as heat, cold, drought, salt and ultraviolet radiation.
Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen in wirtschaftlich bedeutenden transgenen Kulturen von Nutz-und Zierpflanzen, z.B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten.Preferred is the use of the compounds of the invention in economically important transgenic crops of useful and ornamental plants, e.g. of cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables.
Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind.The compounds according to the invention can preferably be employed as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Alternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe gentechnischer Verfahren erzeugt werden (siehe z.B. EP 0221044, EP 0131624). Beschrieben wurden beispielsweise in mehreren Fällen gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z.B. WO 92/011376 A, WO 92/014827 A,Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by genetic engineering techniques (see, for example, EP 0221044, EP 0131624). For example, genetic modifications of crops have been described in several instances to modify the starch synthesized in the plants (e.g., WO 92/011376 A, WO 92/014827 A,
WO 91/019806 A), transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z.B. EP 0 242 236 A, EP 0 242 246 A) oder Glyphosate (WO 92/000377 A) oder der Sulfonylharnstoffe (EP 0 257 993 A, US 5,013,659) oder gegen Kombinationen oder Mischungen dieser Herbizide durch „gene stacking" resistent sind, wie transgenen Kulturpflanzen z. B. Mais oder Soja mit dem Handelsnamen oder der Bezeichnung Optimum™ GAT™ (Glyphosate ALSWO 91/019806 A), transgenic crops which are resistant to certain herbicides of the type Glufosinate (cf., for example, EP 0 242 236 A, EP 0 242 246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0 257 993 A, US Pat. No. 5,013,659) or against combinations or mixtures of these herbicides by gene stacking "are resistant, such as transgenic crops such as corn or soybean with the trade name or the name Optimum ™ GAT ™ (Glyphosate ALS
Tolerant). transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP 0 142 924 A, EP 0 193 259 A). - transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/013972 A). gentechnisch veränderte Kulturpflanzen mit neuen Inhalts- oder Sekundärstoffen z.B. neuen Phytoalexinen, die eine erhöhte Krankheitsresistenz verursachen (EP 0 309 862 A, EP 0 464 461 A) - gentechnisch veränderte Pflanzen mit reduzierter Photorespiration, die höhere Erträge und höhere Stresstoleranz aufweisen (EP 0 305 398 A) transgene Kulturpflanzen, die pharmazeutisch oder diagnostisch wichtige Proteine produzieren („molecular pharming") transgene Kulturpflanzen, die sich durch höhere Erträge oder bessere Qualität auszeichnen transgene Kulturpflanzen die sich durch Kombinationen z.B. der o. g. neuen Eigenschaften auszeichnen („gene stacking")Tolerant). Transgenic crops, such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0 142 924 A, EP 0 193 259 A). transgenic crops with modified fatty acid composition (WO 91/013972 A). genetically engineered crops with new content or secondary substances, e.g. new phytoalexins which cause increased disease resistance (EP 0 309 862 A, EP 0 464 461 A) - genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0 305 398 A) transgenic crops, which are pharmaceutically or diagnostically produce important proteins ("molecular pharming") transgenic crops that are characterized by higher yields or better quality transgenic crops characterized by combinations such as the above new properties ("gene stacking")
Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt; siehe z.B. I. Potrykus und G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, oder Christou, "Trends in Plant Science" 1 (1996) 423-431).Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; see, e.g. I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431).
Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle inFor such genetic manipulations, nucleic acid molecules can be used in
Plasmide eingebracht werden, die eine Mutagenese oder eine Sequenzveränderung durch Rekombination von DNA-Sequenzen erlauben. Mit Hilfe von Standardverfahren können z.B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA-Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden, siehe z.B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2. Aufl. CoId Spring Harbor Laboratory Press, CoId Spring Harbor, NY; oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996Plasmids are introduced which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of For example, standard methods can be used to exchange bases, to remove partial sequences, or to add natural or synthetic sequences. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität eines Genprodukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines Cosuppressionseffektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet.The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense-Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codieredenFor this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. Also possible is the use of DNA sequences encoding a high degree of homology to the ones
Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind.Have sequences of a gene product but are not completely identical.
Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z.B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. 11 (1992), 3219- 3227; Wolter et al., Proc. Natl. Acad. Sei. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991 ), 95-106). Die Expression der Nukleinsäuremoleküle kann auch in den Organellen der Pflanzenzellen stattfinden. Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h., sowohl monokotyle als auch dikotyle Pflanzen.In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. However, to achieve localization in a particular compartment, for example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The expression of the nucleic acid molecules can also take place in the organelles of the plant cells. The transgenic plant cells can be whole by known techniques Plants are regenerated. The transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants.
So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durchThus, transgenic plants are available, the altered properties by
Überexpression, Suppression oder Inhibierung homologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen.Overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.
Vorzugsweise können die erfindungsgemäßen Verbindungen in transgenen Kulturen eingesetzt werden, welche gegen Wuchsstoffe, wie z.B. 2,4 D, Dicamba oder gegen Herbizide, die essentielle Pflanzenenzyme, z.B. Acetolactatsynthasen (ALS), EPSP Synthasen, Glutaminsynthasen (GS) oder Hydoxyphenylpyruvat Dioxygenasen (HPPD) hemmen, respektive gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, der Glyphosate, Glufosinate oder Benzoylisoxazole und analogen Wirkstoffe, oder gegen beliebige Kombinationen dieser Wirkstoffe, resistent sind.Preferably, the compounds of the invention can be used in transgenic cultures which are resistant to growth factors, such as e.g. 2,4 D, dicamba or against herbicides containing essential plant enzymes, e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or Hydoxyphenylpyruvat Dioxygenases (HPPD) inhibit or resistant to herbicides from the group of sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogues, or against any combination of these agents resistant.
Besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen eingesetzt werden, die gegen eine Kombination von Glyphosaten und Glufosinaten, Glyphosaten und Sulfonylharnstoffen oder Imidazolinonen resistent sind. Ganz besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen wie z. B. Mais oder Soja mit dem Handelsnamen oder der Bezeichnung Optimum™ GAT™ (Glyphosate ALS Tolerant) eingesetzt werden.The compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Most preferably, the compounds of the invention in transgenic crops such. As corn or soybean with the trade name or the name Optimum ™ GAT ™ (Glyphosate ALS Tolerant) are used.
Bei der Anwendung der erfindungsgemäßen Verbindungen in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen.In the application of the compounds according to the invention in transgenic crops, in addition to the effects observed in other crops against harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides against which the transgenic culture is resistant, as well as influencing growth and yield of transgenic crops.
Gegenstand der Erfindung ist deshalb auch die Verwendung der erfindungsgemäßen Verbindungen als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen.The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
Die erfindungsgemäßen Verbindungen können z.B. in Form von Spritzpulvern, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, welche die erfindungsgemäßen Verbindungen enthalten.The compounds of the invention may e.g. be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
Die erfindungsgemäßen Verbindungen können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in-Wasser- und Wasser-in-ÖI-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), ULV-Formulierungen, Mikrokapseln und Wachse. Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.The compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag, Munich, 4th edition, 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2πd Ed., interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986.The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are for example, described in Watkins, Handbook of Insecticides Dust Diluents and Carriers, 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2πd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Publishing company, Stuttgart 1976; Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen Pestizid wirksamen Stoffen, wie z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix.On the basis of these formulations, combinations with other pesticidally active substances, such as e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.
Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z.B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt.Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, dibutylnaphthalene-sodium sulfonate or sodium oleoylmethyltaurine. To prepare the wettable powders, the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel z.B. Butanol, Cyclohexanon, Dimethylformamid, XyIoI oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z.B. Polyoxyethylensorbitanfettsäureester.Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). As emulsifiers For example, it is possible to use alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxethylenesorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde.Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. are already listed above for the other formulation types.
Emulsionen, z.B. ÖI-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wässrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen.Emulsions, e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described, for example, in US Pat. listed above for the other formulation types.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt. Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B. Verfahren in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemicai and Engineering 1967, Seiten 147 ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, S. 8-57.Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of plate, fluidized bed, extruder and spray granules, see for example methods in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemicai and Engineering 1967, pages 147 ff; Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z.B. G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , Seiten 81-96 und J. D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103.For further details on the formulation of crop protection agents see, e.g. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
Die agrochemischen Zubereitungen enthalten in der Regel 0.1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, erfindungsgemäße Verbindungen.The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
In Spritzpulvern beträgt die Wirkstoffkonzentration z.B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0.05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%.In wettable powders, the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
Daneben enthalten die genannten Wirkstoffformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel.In addition, the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
Als Kombinationspartner für die erfindungsgemäßen Verbindungen inAs a combination partner for the compounds of the invention in
Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, wie Insektizide, Fungizide, Pflanzenwachstumsregulatoren oder Herbizide geeignet. Beispiele derartiger Herbizide sind solche, die auf einer Inhibition von beispielsweise Acetolactat-Synthase, Acetyl-CoA-Carboxylase, Cellulose-Synthase, Enolpyruvylshikimat-3-phosphat-Synthase, Glutamin- Synthetase, p-Hydroxyphenylpyruvat-Dioxygenase, Phytoendesaturase,Mixture formulations or in the tank mix are known, for example Active ingredients such as insecticides, fungicides, plant growth regulators or herbicides suitable. Examples of such herbicides are those which are based on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase,
Photosystem I, Photosystem II, Protoporphyrinogen-Oxidase beruhen, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441 445 oder "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 und dort zitierter Literatur beschrieben sind. Als bekannte Herbizide oder Pflanzenwachstumsregulatoren, die mit den erfindungsgemäßen Verbindungen kombiniert werden können, sind z.B. folgende Wirkstoffe zu nennen (die Verbindungen sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen oder mit der Codenummer bezeichnet) und umfassen stets sämtliche Anwendungsformen wie Säuren, Salze, Ester und Isomere wie Stereoisomere und optische Isomere. Dabei sind beispielhaft eine und zum Teil auch mehrere Anwendungsformen genannt:Photosystem I, photosystem II, protoporphyrinogen oxidase, can be used, as e.g. from Weed Research 26 (1986) 441,445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and cited therein. As known herbicides or plant growth regulators which can be combined with the compounds according to the invention are e.g. the following active ingredients (the compounds are denoted either by the "common name" according to the International Organization for Standardization (ISO) or the chemical name or with the code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers. Here are an example and partly also called several application forms:
Acetochlor, Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen-natrium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-natrium, Ametryn,Acetochlor, Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen Sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim Sodium, Ametryn,
Amicarbazone, Amidochlor, Amidosulfuron, Aminocyclopyrachlor, Aminopyralid, Amitrole, Ammoniumsulfamat, Ancymidol, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, Beflubutamid, Benazolin, Benazolin-ethyl, bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron-methyl, Bentazone, Benzfendizone,Amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, atrazines, azafenidine, azimsulfuron, aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS- 776H, beflubutamide, benazoline, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron-methyl, bentazone, benzfendizone,
Benzobicyclon, Benzofenap, Benzofluor, Benzoylprop, Bifenox, Bilanafos, Bilanafos- natrium, Bispyribac, Bispyribac-natrium, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrole, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorbromuron, Chlorbufam, Chlorfenac, Chlorfenac-natrium, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chlorid, Chlornitrofen, Chlorophthalim, Chlorthal- dimethyl, Chlorotoluron, Chlorsulf uron, Cinidon, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop Clodinafop-propargyl, Clofencet, Clomazone, Clorneprop, Cioprop, Ciopyraiid, Cioransuiam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim,Benzobicyclone, Benzofenap, Benzofluor, Benzoylprop, Bifenox, Bilanafos, Bilanafos-Sodium, Bispyribac, Bispyribac Sodium, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butraline, Butroxydim, Butylates, Cafenstrole, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorobromuron, Chlorbufam, Chlorfenac, Chlorfenac sodium, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chloride, Chlornitrofen, Chlorophthalim, Chlorthal-dimethyl, Chlorotoluron, Chlorsulf uron, Cinidon, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop Clodinafop-propargyl, Clofencet, Clomazone, Clorneprop, Cioprop, Ciopyraiid, Cioransuiam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim,
Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2,4-D, 2,4- DB, Daimuron/Dymron, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP), Diallate, Dicamba, Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diclofop-methyl, Diclofop-P-methyl, Diclosulam, Diethatyl, Diethatyl-ethyl, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Diflufenzopyr- natrium, Dimefuron, Dikegulaonatrium, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimethipin, Dimetrasulfuron, Dinitramine, Dinoseb, Dinoterb, Diphenamid, Dipropetryn, Diquat, Diquat-dibromide, Dithiopyr, Diuron, DNOC, Eglinazine-ethyl, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron-methyl, Ethephon, Ethidimuron, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen-ethyl, Ethoxysulfuron, Etobenzanid, F-5331 , d.h. N-[2-Chlor-4-fluor-5-[4- (3-fluorpropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-ethansulfonamid, Fenoprop, Fenoxaprop, Fenoxaprop-P, Fenoxaprop-ethyl, Fenoxaprop-P-ethyl, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop-butyl, Fluazifop-P-butyl, Fluazolate, Flucarbazone, Flucarbazone-natrium, Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpyr, Flufenpyr-ethyl, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Flumipropyn, Fluometuron, Fluorodifen, Fluoroglycofen, Fluoroglycofen-ethyl, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-methyl-natrium, Flurenol, Flurenol- butyl, Fluridone, Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet, Fluthiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxyfen, Gibberellinsäure, Glufosinate, Glufosinate- ammonium, Glufosinate-P, Glufosinate-P-ammonium, Glufosinate-P-natrium, Glyphosate, Glyphosate-isopropylammonium, H-9201 , Halosafen, Halosulfuron, Halosulfuron-methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-ethoxyethyl, Haloxyfop-P- ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P-methyl, Hexazinone, HNPC-9908, HW- 02, Imazamethabenz, Imazamethabenz-methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Inabenfide, Indanofan, Indaziflam, Indolessigsäure (IAA), 4-lndol-3-ylbuttersäure (IBA), lodosulfuron, lodosulfuron- methyi-natrium, ioxynii, ipfencarbazone, Isocarbamid, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, KUH-043, KUH-071 , Karbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, Maleinsäurehydrazid, MCPA, MCPB, MCPB-methyl, -ethyl und -natrium, Mecoprop, Mecoprop-natrium, Mecoprop- butotyl, Mecoprop-P-butotyl, Mecoprop-P-dimethylammonium, Mecoprop-P-2- ethylhexyl, Mecoprop-P-kalium, Mefenacet, Mefluidide, Mepiquat-chlorid, Mesosulfuron, Mesosulfuron-methyl, Mesotrione, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Methazole, Methiozolin, Methoxyphenone, Methyldymron, 1-Methylcyclopropen, Methylisothiocyanat, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulf uron-methyl, Molinate, Monalide, Monocarbamide, Monocarbamide-dihydrogensulfat, Monolinuron, Monosulfuron, Monuron, MT 128, MT-5950, d. h. N-[3-Chlor-4-(1-methylethyl)-phenyl]-2-methylpentanamid, NGGC- 011 , Naproanilide, Napropamide, Naptalam, NC-310, d.h. 4-(2,4-dichlorobenzoyl)-1- methyl-5-benzyloxypyrazole, NC-620, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Nitrophenolat-natrium (Isomerengemisch), Nitrofluorfen, Nonansäure, Norflurazon, Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paclobutrazol, Paraquat, Paraquat- dichlorid, Pelargonsäure (Nonansäure), Pendimethalin, Pendralin, Penoxsulam, Pentanochlor, Pentoxazone, Perfluidone, Pethoxamid, Phenisopham, Phenmedipham, Phenmedipham-ethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenop-butyl, Pretilachlor, Primisulfuron, Primisulfuron- methyl, Probenazole, Profluazol, Procyazine, Prodiamine, Prifluraline, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propoxycarbazone-natrium, Propyrisulfuron, Propyzamide, Prosulfalin, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen- ethyl, Pyrasulfotole, Pyrazolynate (Pyrazolate), Pyrazosulfuron-ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-isopropyl, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobac-methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac-natrium, Pyroxasulfone, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Saflufenacil, Secbumeton, Sethoxydim, Siduron, Simazine, Simetryn, SN-106279, Sulcotrione, Sulfallate (CDEC), Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosate (Glyphosate-trimesium), Sulfosulfuron, SYN-449, SYN-523, SYP-249, SYP-298, SYP-300, Tebutam, Tebuthiuron, Tecnazene, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazafluron, Thiazopyr, Thidiazimin, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, Thifensulfuron, Thifensulfuron-methyl, Thiobencarb, Tiocarbazil, Topramezone, Tralkoxydim, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Tribenuron-methyl, Trichloressigsäure (TCA), Triclopyr, Tridiphane, Trietazine, Trifloxysulfuron, Trifloxysulfuron-natrium, Trifluralin, Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapac, Trinexapac-ethyl, Tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 sowie die folgenden VerbindungenCycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2,4-D, 2,4-DB, Daimurone / Dymron, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP) , Dialkylates, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethatyl, diethyl-ethyl, difenoxuron, difenzoquat, diflufenican, difluufenzopyr, difluorobenzopyr-sodium, dimefuron, dic- gula sodium, dimefuron , Dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipine, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPTC, esprocarb, ethalfluralin , Ethametsulfuron-methyl, ethephon, ethidimuron, ethiozine, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, F-5331, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) - 4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, fenoprop, fenoxaprop, fenox aprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P butyl, fluazolates, flucarbazone, flucarbazone sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr, flufenpyrethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazine, flumipropyne, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam , Flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, flurenol, flurenolbutyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamine, furyloxyfen , Gibberellin, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron, halosulfur on-methyl, haloxyfop, haloxyfop-P, haloxyfopethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HNPC-9908, HW 02, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, inabenfide, indanofan, indaziflam, indoleacetic acid (IAA), 4-indol-3-yl-butyric acid (IBA), iodosulfuron, iodosulfuron-methyl-sodium, ioxynii, ipfencarbazone, isocarbamide, isopropalin, isoproturon, isourone, isoxaben, isoxachlorotolene, isoxaflutole, isoxapyrifop, KUH-043, KUH-071, carbutilate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and sodium, mecoprop, mecoprop-sodium, mecopropbutotyl, mecoprop-p-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidides, mepiquat chloride, mesosulfuron, Mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, methazoles, methiozoline, methoxyphenones, methyldymron, 1-methylcyclopropene, methylisothiocyanate, metobenzuron, metobromuron, metolachlor, s-metolachlor, metosulam, metoxuron, metribuzin, metsul furon, metsulfuron-methyl, molinates, monalides, monocarbamides, monocarbamic dihydrogen sulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, ie N- [3-chloro-4- (1-methylethyl) -phenyl] -2 -methylpentanamide, NGGC-011, naproanilides, napropamide, naptalam, NC-310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazoles, NC-620, neburone, nicosulfuron, nipyraclofen, nitrite, nitrofen, Nitrophenolate sodium (isomeric mixture), nitrofluorfen, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefones, oxyfluorfen, paclobutrazole, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, Pentoxazone, Perfluidone, Pethoxamide, Phenisopham, Phenmedipham, Phenmediphamethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenop-butyl, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazoles, Profluazole, Procyazine, Prodiamine, Prifluralines, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometry, Propachlor, Propanil, Propaquizafop, Propazine, Prophet, Propisochlor, Propoxycarbazone, Propoxycarbazone-Sodium, Propyrisulfuron, Propyzamide, Prosulfine, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen-ethyl, Pyrasulfotole, Pyrazolynates (pyrazolates), pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribenzoxime, pyributicarb, pyridafol, Pyridates, Pyridalid, Pyriminobac, Pyriminobac-methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac-Sodium, Pyroxasulfones, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, saflufenacil, secbumetone, sethoxydim, siduron, simazine, simetryn, SN-106279, sulctotrione, sulfallates (CDEC), sulentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SYN-449, SYN-523, SYP-249, SYP-298, SYP-300, Tebutam, Tebuthiuron, Tecnazene, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumetone, Terbuthylazine, Terbutryn, Thenylchloro, Thiafluamide, Thiazafluron, Thiazopyr, Thidiazimine, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, toramezone, tralkoxydim, triallate, triasulfuron, triaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tri diphanes, trietazines, trifloxysulfuron, trifloxysulfuron sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 and the following compounds
Von besonderem Interesse ist die selektive Bekämpfung von Schadpflanzen in Kulturen von Nutz- und Zierpflanzen. Obgleich die erfindungsgemäßen Verbindungen bereits in vielen Kulturen sehr gute bis ausreichende Selektivität aufweisen, können prinzipiell in einigen Kulturen und vor allem auch im Falle von Mischungen mit anderen Herbiziden, die weniger selektiv sind, Phytotoxizitäten an den Kulturpflanzen auftreten. Diesbezüglich sind Kombinationen von besonderem Interesse, welche die erfindungsgemäßen Verbindungen in Kombination mit Safenern enthalten, sowie gegebenenfalls weitere Pestizide wie Herbizide. Die Safener, welche in einem antidotisch wirksamen Gehalt eingesetzt werden, reduzieren die phytotoxischen Nebenwirkungen der eingesetzten Pestizide, z. B. in wirtschaftlich bedeutenden Kulturen wie Getreide (z.B. Weizen, Gerste, Roggen, Mais, Reis, Hirse), Zuckerrübe, Zuckerrohr, Raps, Baumwolle und Soja, vorzugsweise Getreide.Of particular interest is the selective control of harmful plants in crops of commercial and ornamental plants. Although the compounds according to the invention already have very good to sufficient selectivity in many cultures, phytotoxicities can in principle occur in the crop plants in some crops and, above all, in the case of mixtures with other herbicides which are less selective. In this regard, combinations of particular interest, which contain the compounds of the invention in combination with safeners, and optionally other pesticides such as herbicides. The safeners, which are used in an antidote effective content, reduce the phytotoxic side effects of pesticides used, eg. In economically significant crops such as cereals (e.g., wheat, barley, rye, corn, rice, millet), sugar beet, sugarcane, oilseed rape, cotton and soybeans, preferably cereals.
Folgende Gruppen von Verbindungen kommen beispielsweise als Safener in Frage:The following groups of compounds are suitable, for example, as safeners:
S1 ) Verbindungen aus der Gruppe heterocyclischer Carbonsäurederivate: S1a) Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure (S1a), vorzugsweise Verbindungen wieS1) Compounds from the group of heterocyclic carboxylic acid derivatives: S1 a ) Compounds of the type of dichlorophenylpyrazoline-3-carboxylic acid (S1 a ), preferably compounds such as
1-(2,4-Dichloφhenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carbonsäure, 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carbonsäure- ethylester (S1-1) ("Mefenpyr-diethyl"), und verwandte Verbindungen, wie sie in der WO-A-91 /07874 beschrieben sind;1- (2,4-Dichloro-phenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid, 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2- pyrazoline-3-carboxylic acid ethyl ester (S1-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874;
Si b) Derivate der Dichlorphenylpyrazolcarbonsäure (S1 b), vorzugsweise Verbindungen wieSi b ) Derivatives of Dichlorphenylpyrazolcarbonsäure (S1 b ), preferably compounds such
1-(2,4-Dichlorphenyl)-5-methylpyrazol-3-carbonsäureethylester (S1-2), 1-(2,4-Dichlorphenyl)-5-isopropylpyrazol-3-carbonsäureethylester (S1-3), 1-(2,4-Dichlorphenyl)-5-(1 ,1-dimethyl-ethyl)pyrazol-3-carbonsäureethylester (S1-4) und verwandte Verbindungen, wie sie in EP-A-333 131 und EP-A-269 806 beschrieben sind;Ethyl 1- (2,4-dichlorophenyl) -5-methylpyrazole-3-carboxylate (S1-2), 1- (2,4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylic acid ethyl ester (S1-3), 1- (2 , 4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds as described in EP-A-333,131 and EP-A-269,806;
S1C) Derivate der 1 ,5-Diphenylpyrazol-3-carbonsäure (S1C), vorzugsweise Verbindungen wieS1 C ) derivatives of 1, 5-diphenylpyrazole-3-carboxylic acid (S1 C ), preferably compounds such as
1 -(2,4-Dichlorphenyl)-5-phenylpyrazol-3-carbonsäureethylester (S1 -5), 1 -(2-Chlorphenyl)-5-phenylpyrazol-3-carbonsäuremethylester (S 1 -6) und verwandte Verbindungen wie sie beispielsweise in der EP-A-268554 beschrieben sind;1 - (2,4-Dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (S1 -5), 1- (2-chlorophenyl) -5-phenylpyrazole-3-carboxylic acid methyl ester (S 1 -6) and related compounds as, for example in EP-A-268554;
S1d) Verbindungen vom Typ der Triazolcarbonsäuren (S1d), vorzugsweise Verbindungen wie Fenchlorazol(-ethylester), d.h.S1 d ) compounds of the type of triazolecarboxylic acids (S1 d ), preferably compounds such as fenchlorazole (ethyl ester), ie
1 -(2,4-Dichlorphenyl)-5-trichlormethyl-(1 H)-1 ,2,4-triazol-3-carbonsäure- ethylester (S1-7), und verwandte Verbindungen, wie sie in EP-A-174 562 und EP-A-346 620 beschrieben sind;1- (2,4-dichlorophenyl) -5-trichloromethyl- (1H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (S1-7) and related compounds as described in EP-A-174 562 and EP-A-346 620;
S1e) Verbindungen vom Typ der 5-Benzyl- oder 5-Phenyl-2-isoxazolin-3- carbonsäure, oder der 5,5-Diphenyl-2-isoxazolin-3-carbonsäure (S1e), vorzugsweise Verbindungen wieS1 e) Compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid, or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 e), preferably compounds such as
5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (S1 -8) oder 5-Phenyl-2-isoxazolin-3-carbonsäureethylester (S1-9) und verwandte Verbindungen, wie sie in WO-A-91 /08202 beschrieben sind, bzw.5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S1 -8) or 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9) and related compounds as described in WO-A- 91/08202, respectively
5,5-Diphenyl-2-isoxazolin-carbonsäure (S1-10) oder 5,5-Diphenyl-2- isoxazolin-carbonsäureethylester (S1-11 ) ("Isoxadifen-ethyl") oder -n-propylester (S1-12) oder der 5-(4-Fluorphenyl)-5-phenyl-2-isoxazolin-3- carbonsäureethylester (S1-13), wie sie in der Patentanmeldung WO-A-95/07897 beschrieben sind.5,5-Diphenyl-2-isoxazoline-carboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazoline-carboxylic acid ethyl ester (S1-11) ("isoxadifen-ethyl") or n-propyl ester (S1-12) or 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13), as described in the patent application WO-A-95/07897 ,
S2) Verbindungen aus der Gruppe der 8-Chinolinyloxyderivate (S2):S2) Compounds from the group of 8-quinolinyloxy derivatives (S2):
S2a) Verbindungen vom Typ der 8-Chinolinoxyessigsäure (S2a), vorzugsweise (5-Chlor-8-chinolinoxy)essigsäure-(1-methylhexyl)-ester ("Cloquintocet- mexyl") (S2-1), (5-Chlor-8-chinolinoxy)essigsäure-(1 ,3-dimethyl-but-1-yl)-ester (S2-2), (5-Chlor-8-chinolinoxy)essigsäure-4-allyl-oxy-butylester (S2-3), (5-Chlor-8-chinolinoxy)essigsäure-1 -allyloxy-prop-2-ylester (S2-4),S2 a ) compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably (5-chloro-8-quinolinoxy) acetic acid (1-methylhexyl) ester ("cloquintocetmexyl") (S2-1), (5- Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyl oxy-butyl ester (S2- 3), (5-chloro-8-quinolinoxy) acetic acid 1 -allyloxy-prop-2-yl ester (S2-4),
(5-Chlor-8-chinolinoxy)essigsäureethylester (S2-5), (5-Chlor-8-chinolinoxy)essigsäuremethylester (S2-6), (5-Chlor-8-chinolinoxy)essigsäureallylester (S2-7), (5-Chlor-8-chinolinoxy)essigsäure-2-(2-propyliden-iminoxy)-1-ethylester (S2-8), (5-Chlor-8-chinolinoxy)essigsäure-2-oxo-prop-1 -ylester (S2-9) und verwandte Verbindungen, wie sie in EP-A-86 750, EP-A-94 349 und EP-A-191 736 oder EP-A-O 492 366 beschrieben sind, sowie (5-Chlor-8- chinolinoxy)essigsäure (S2-10), deren Hydrate und Salze, beispielsweise deren Lithium-, Natrium- Kalium-, Kalzium-, Magnesium-, Aluminium-, Eisen-, Ammonium-, quartäre Ammonium-, Sulfonium-, oder Phosphoniumsalze wie sie in der WO-A-2002/34048 beschrieben sind;(5-Chloro-8-quinolinoxy) acetic acid ethyl ester (S2-5), (5-chloro-8-quinolinoxy) acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy) allyl acetate (S2-7), (5 -Chloro-8-quinolinoxy) acetic acid 2- (2-propylidene-iminoxy) -1-ethyl ester (S2-8), (5-chloro-8-quinolinoxy) -acetic acid 2-oxo-prop-1-yl-ester (S2 -9) and related compounds as described in EP-A-86,750, EP-A-94,349 and EP-A-191,736 or EP-A-492,366, as well as (5-chloro-8-quinolinoxy) acetic acid (S2-10), their hydrates and salts, for example their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO -A-2002/34048;
S2b) Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)malonsäure (S2b), vorzugsweise Verbindungen wie (5-Chlor-8-chinolinoxy)malonsäure- diethylester, (5-Chlor-8-chinolinoxy)malonsäurediallylester,S2 b ) compounds of the (5-chloro-8-quinolinoxy) malonic acid type (S2 b ), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester,
(5-Chlor-8-chinolinoxy)malonsäure-methyl-ethylester und verwandte Verbindungen, wie sie in EP-A-O 582 198 beschrieben sind.(5-chloro-8-quinolinoxy) malonic acid methyl ethyl ester and related compounds as described in EP-A-0 582 198.
S3) Wirkstoffe vom Typ der Dichloracetamide (S3), die häufig als Vorauflauf- safener (bodenwirksame Safener) angewendet werden, wie z. B.S3) Active substances of the dichloroacetamide type (S3), which are often used as pre-emergence safener (soil-active safener), such as. B.
"Dichlormid" (N,N-Diallyl-2,2-dichloracetamid) (S3-1 ), "R-29148" (3-Dichloracetyl-2,2,5-trimethyl-1 ,3-oxazolidin) der Firma Stauffer (S3-2),"Dichloromid" (N, N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2),
"R-28725" (3-Dichloracetyl-2,2,-dimethyl-1 ,3-oxazolidin) der Firma Stauffer"R-28725" (3-dichloroacetyl-2,2, -dimethyl-1,3-oxazolidine) from Stauffer
(S3-3),(S3-3),
"Benoxacor" (4-Dichloracetyl-3,4-dihydro-3-methyl-2H-1 ,4-benzoxazin) (S3-4),"Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
"PPG-1292" (N-Allyl-N-[(1 ,3-dioxolan-2-yl)-methyl]-dichloracetamid) der Firma"PPG-1292" (N-allyl-N - [(1,3-dioxolan-2-yl) -methyl] -dichloroacetamide) from the company
PPG Industries (S3-5),PPG Industries (S3-5),
"DKA-24" (N-Allyl-N-KallylaminocarbonyOmethyll-dichloracetamid) der Firma"DKA-24" (N-allyl-N-kallylaminocarbonylmethyll-dichloroacetamide) from the company
Sagro-Chem (S3-6),Sagro-Chem (S3-6),
"AD-67" oder "MON 4660" (3-Dichloracetyl-1-oxa-3-aza-spiro[4,5]decan) der"AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) of
Firma Nitrokemia bzw. Monsanto (S3-7),Company Nitrokemia or Monsanto (S3-7),
"TI-35" (1-Dichloracetyl-azepan) der Firma TRI-Chemical RT (S3-8),"TI-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8),
"Diclonon" (Dicyclonon) oder "BAS145138" oder "LAB145138" (S3-9)"Diclonone" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9)
(3-Dichloracetyl-2,5,5-trimethyl-1 ,3-diazabicyclo[4.3.0]nonan) der Firma(3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo [4.3.0] nonane) from the company
BASF,BASF,
"Furilazol" oder "MON 13900" ((RS)-3-Dichloracetyl-5-(2-furyl)-2,2-dimethyl- oxazolidin) (S3-10), sowie dessen (R)-Isomer (S3-11 )."Furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyl-oxazolidine) (S3-10), as well as its (R) -isomer (S3-11 ).
S4) Verbindungen aus der Klasse der Acylsulfonamide (S4): S4a) N-Acylsulfonamide der Formel (S4a) und deren Salze wie sie in der WO-A-97/45016 beschrieben sind,S4) Compounds of the class of the acylsulfonamides (S4): S4 a ) N-acylsulfonamides of the formula (S4 a ) and salts thereof as described in WO-A-97/45016,
worinwherein
RA1 (CrCβJAlkyl, welches durch vA Substituenten aus der Gruppe Halogen, (Ci-C4)Alkoxy, (CrCβJHaloalkoxy und (CrC4)Alkylthio und im Falle cyclischer Reste auch durch (CrC4)Alkyl und (CrC4)Haloalkyl substituiert ist; RA2 Halogen, (CrC4)Alkyl, (C1-C4)AIkOXy, CF3; RA 1 (CrCβJAlkyl which substituted by v A substituents from the group halogen, (Ci-C 4) alkoxy, (CrCβJHaloalkoxy and (CrC 4) alkylthio and in case of cyclic radicals, also by (CrC 4) alkyl and (CrC 4) haloalkyl is; RA 2 is halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, CF 3;
ΠΓIA 1 oder 2;ΠΓIA 1 or 2;
VA ist 0, 1 , 2 oder 3 bedeuten;VA is 0, 1, 2 or 3;
S4b) Verbindungen vom Typ der 4-(Benzoylsulfamoyl)benzamide der Formel (S4b) und deren Salze, wie sie in der WO-A-99/16744 beschrieben sind,S4 b) Compounds of the 4- (benzoylsulfamoyl) benzamide of the formula (S4 b) and salts thereof, as they are in the WO-A-99/16744 describes
worinwherein
RB1, RB2 unabhängig voneinander Wasserstoff, (Ci-C6)Alkyl,RB 1 , RB 2 independently of one another are hydrogen, (C 1 -C 6 ) -alkyl,
(C3-C6)Alkenyl, (C3-C6)Alkinyl,(C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl,
RB3 Halogen, (CrC4)Alkyl, (CrC4)Haloalkyl oder (Ci -C4)AI koxy und mβ 1 oder 2 bedeuten,RB 3 is halogen, (C r C 4 ) alkyl, (C r C 4 ) haloalkyl or (Ci-C 4 ) Al koxy and mβ is 1 or 2,
z.B. solche worine.g. such
1 _1 _
RB1 = Cyclopropyl, RB 2 = Wasserstoff und (RB 3) = 2-OMe istRB 1 = cyclopropyl, R B 2 = hydrogen and (R B 3 ) = 2-OMe
(S4-1 , "Cyprosulfamide",),(S4-1, "Cyprosulfamide"),
RB1 = Cyclopropyl, RB 2 = Wasserstoff und (RB 3) = 5-CI-2-OMe ist (S4-2), RB1 = Ethyl, RB2 = Wasserstoff und (RB 3) = 2-OMe ist (S4-3), RB1 = Isopropyl, R8 2 = Wasserstoff und (RB 3) = 5-CI-2-OMe ist (S4-4) undRB 1 = cyclopropyl, R B 2 = hydrogen and (R B 3 ) = 5-CI-2-OMe is (S4-2), RB 1 = ethyl, RB 2 = hydrogen and (R B 3 ) = 2-OMe is (S4-3), RB 1 = isopropyl, R 8 2 = hydrogen and (R B 3 ) = 5-CI-2-OMe is (S4-4) and
R **BEB111 = Isopropyl, RB 2 = Wasserstoff und (RB 3) = 2-OMe ist (S4-5).R ** B E B 111 = isopropyl, R B 2 = hydrogen and (R B 3 ) = 2-OMe (S4-5).
S4C) Verbindungen aus der Klasse der Benzoylsulfamoylphenylharnstoffe der Formel (S4C), wie sie in der EP-A-365484 beschrieben sind S4 C ) compounds from the class of Benzoylsulfamoylphenylharnstoffe of formula (S4 C ), as described in EP-A-365484
worinwherein
Rc1, Rc2 unabhängig voneinander Wasserstoff, (d-C8)Alkyl, (C3-C6)Alkenyl, (C3-C6)Alkinyl,Rc 1 , Rc 2 independently of one another are hydrogen, (C 1 -C 8 ) alkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl,
Rc3 Halogen, (CrC4)Alkyl, (CrC4)Alkoxy, CF3 mc 1 oder 2 bedeuten;Rc 3 is halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, CF 3 m c is 1 or 2;
beispielsweise 1 -[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylharnstoff,for example, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea,
1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylharnstoff, 1-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylharnstoff.1- [4- (N-2-Methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea.
55) Wirkstoffe aus der Klasse der Hydroxyaromaten und der aromatisch- aliphatischen Carbonsäurederivate (S5), z.B.55) Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g.
3,4,5-Triacetoxybenzoesäureethylester, 3,5-Dimethoxy-4-hydroxybenzoe- säure, 3,5-Dihydroxybenzoesäure, 4-Hydroxysalicylsäure, 4-Fluorsalicycl- säure, 2-Hydroxyzimtsäure, 2,4-Dichlorzimtsäure, wie sie in der WO-A-2004/084631 , WO-A-2005/015994, WO-A-2005/016001 beschrieben sind.3,4,5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in US Pat WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001 are described.
56) Wirkstoffe aus der Klasse der 1 ,2-Dihydrochinoxalin-2-one (S6), z.B. 1-Methyl-3-(2-thienyl)-1 ,2-dihydrochinoxalin-2-on, 1-Methyl-3-(2-thienyl)-1 ,2- dihydrochinoxalin-2-thion, 1 -(2-Aminoethyl)-3-(2-thienyl)-1 ,2-dihydro- chinoxalin-2-on-hydrochlorid, 1-(2-Methylsulfonylaminoethyl)-3-(2-thienyl)-1 ,2- dihydro-chinoxalin-2-on, wie sie in der WO-A-2005/112630 beschrieben sind. S7) Verbindungen aus der Klasse der Diphenylmethoxyessigsäurederivate (S7), z.B. Diphenylmethoxyessigsäuremethylester (CAS-Reg.Nr. 41858-19-9) (S7-1), Diphenylmethoxyessigsäureethylester oder Diphenylmethoxy- essigsäure wie sie in der WO-A-98/38856 beschrieben sind.56) active compounds from the class of 1, 2-dihydroquinoxalin-2-ones (S6), for example 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1-methyl-3- ( 2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxalin-2-one hydrochloride, 1- (2- Methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydro-quinoxalin-2-one as described in WO-A-2005/112630. S7) Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), for example methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid as described in WO-A-98/38856 are.
S8) Verbindungen der Formel (S8),wie sie in der WO-A-98/27049 beschrieben sindS8) compounds of the formula (S8) as described in WO-A-98/27049
worin die Symbole und Indizes folgende Bedeutungen haben:wherein the symbols and indices have the following meanings:
RD 1 ist Halogen, (Ci-C4)Alkyl, (d-C4)Haloalkyl, (Ci-C4)Alkoxy,R D 1 is halogen, (Ci-C 4) alkyl, (dC 4) haloalkyl, (Ci-C 4) alkoxy,
(CrC4)Haloalkoxy,(C r C 4 ) haloalkoxy,
RD2 ist Wasserstoff oder (CrC4)AlkylRD 2 is hydrogen or (C r C 4 ) alkyl
RD3 ist Wasserstoff, (CrC8)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, oder Aryl, wobei jeder der vorgenannten C-haltigen Reste unsubstituiert oder durch einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Reste aus der Gruppe, bestehend aus Halogen und Alkoxy substituiert ist; oder deren Salze no ist eine ganze Zahl von 0 bis 2.RD 3 is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy is substituted; or their salts no is an integer from 0 to 2.
S9) Wirkstoffe aus der Klasse der 3-(5-Tetrazolylcarbonyl)-2-chinolone (S9), z.B. 1 ,2-Dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-chinolon (CAS-Reg. Nr. 219479-18-2), 1 ,2-Dihydro-4-hydroxy-1-methyl-3-(5-tetrazolyl- carbonyl)-2-chinolon (CAS-Reg. Nr. 95855-00-8), wie sie in der WO-A-1999/000020 beschrieben sind.S9) Agents from the class of 3- (5-tetrazolylcarbonyl) -2-quinolones (S9), e.g. 1,2-Dihydro-4-hydroxy-1-ethyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No. 219479-18-2), 1, 2-dihydro-4-hydroxy-1 -methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS reg. no. 95855-00-8), as described in WO-A-1999/000020.
S10) Verbindungen der Formeln (S10a) oder (S10b) wie sie in der WO-A-2007/023719 und WO-A-2007/023764 beschrieben sind S10) compounds of the formulas (S10 a ) or (S10 b ) as described in WO-A-2007/023719 and WO-A-2007/023764
( S10a ) ( S10b )(S10 a) (S10 b)
worinwherein
RE1 Halogen, (C1-C4)AIkYl1 Methoxy, Nitro, Cyano, CF3, OCF3 RE 1 is halogen, (C 1 -C 4) -alkyl 1 is methoxy, nitro, cyano, CF 3, OCF 3
YE, ZE unabhängig voneinander O oder S, nE eine ganze Zahl von 0 bis 4,YE, Z E independently of one another are O or S, n E is an integer from 0 to 4,
RE2 (Ci-Ci6)Alkyl, (C2-C6)Alkenyl, Aryl, Benzyl, Halogenbenzyl,RE 2 (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, aryl, benzyl, halobenzyl,
RE3 Wasserstoff oder (d-CβJAlkyl bedeuten.RE 3 is hydrogen or (d-CβJAlkyl mean.
S11 ) Wirkstoffe vom Typ der Oxyimino-Verbindungen (S11 ), die als Saatbeizmittel bekannt sind, wie z. B.S11) oxyimino compound type compounds (S11) known as seed dressings, such as those described in US Pat. B.
"Oxabetrinil" ((Z)-1 ,3-Dioxolan-2-ylmethoxyimino (phenyl)acetonitril) (S11-1 ), das als Saatbeiz-Safenerfür Hirse gegen Schäden von Metolachlor bekannt ist,"Oxabetrinil" ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed dressing safener for millet against damage by metolachlor,
"Fluxofenim" (1 -(4-Chlorphenyl)-2,2,2-trifluor-1 -ethanon-O-(1 ,3-dioxolan-2- ylmethyl)-oxim) (S11-2), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist, und"Fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) -oxime) (S11-2) which was used as seed dressing Safener for millet is known against damage from metolachlor, and
"Cyometrinil" oder "CGA-43089" ((Z)-Cyanomethoxyimino(phenyl)acetonitril) (S11-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist."Cyometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile) (S11-3), which is known as a seed dressing safener for millet against damage by metolachlor.
S12) Wirkstoffe aus der Klasse der Isothiochromanone (S12), wie z.B. Methyl-[(3- oxo-1 H-2-benzothiopyran-4(3H)-yliden)methoxy]acetate (CAS-Reg. Nr. 205121 -04-6) (S12-1 ) und verwandte Verbindungen aus WO-A-1998/13361. 513) Eine oder mehrere Verbindungen aus Gruppe (S13):S12) active substances from the class of the isothiochromanones (S12), such as, for example, methyl - [(3-oxo-1H-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS Reg. No. 205121 -04- 6) (S12-1) and related compounds of WO-A-1998/13361. 513) One or more compounds from group (S13):
"Naphthalic anhydrid" (1 ,8-Naphthalindicarbonsäureanhydrid) (S13-1 ), das als"Naphthalene anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as
Saatbeiz-Safener für Mais gegen Schäden von Thiocarbamatherbiziden bekannt ist, "Fenclorim" (4,6-Dichlor-2-phenylpyrimidin) (S13-2), das als Safener fürSeizebeiz-Safener for corn is known against damage of thiocarbamate herbicides, "Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is used as a safener for
Pretilachlor in gesätem Reis bekannt ist,Pretilachlor is known in sown rice,
"Flurazole" (Benzyl-2-chlor-4-trifluormethyl-1 ,3-thiazol-5-carboxylat) (S13-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Alachlor und"Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3) used as a seed dressing safener for millet against damage by alachlor and
Metolachlor bekannt ist, "CL 304415" (CAS-Reg. Nr. 31541 -57-8)Metolachlor is known, "CL 304415" (CAS Reg. No. 31541 -57-8)
(4-Carboxy-3,4-dihydro-2H-1-benzopyran-4-essigsäure) (S13-4) der Firma(4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) of the company
American Cyanamid, das als Safener für Mais gegen Schäden vonAmerican Cyanamid, which acts as a safener for maize against damage from
Imidazolinonen bekannt ist,Imidazolinones are known
11MG 191" (CAS-Reg. Nr. 96420-72-3) (2-Dichlormethyl-2-methyl-1 ,3-dioxolan) (S13-5) der Firma Nitrokemia, das als Safener für Mais bekannt ist, 11 MG 191 "(CAS reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn,
"MG-838" (CAS-Reg. Nr. 133993-74-5)"MG-838" (CAS Reg. No. 133993-74-5)
(2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) der Firma(2-propenyl 1-oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) from the company
NitrokemiaNitrokemia
"Disulfoton" (O,O-Diethyl S-2-ethylthioethyl phosphordithioat) (S13-7), "Dietholate" (O,O-Diethyl-O-phenylphosphorothioat) (S13-8),"Disulfone" (O, O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), "dietholate" (O, O-diethyl-O-phenyl phosphorothioate) (S13-8),
"Mephenate" (4-Chlorphenyl-methylcarbamat) (S13-9)."Mephenate" (4-chlorophenyl methylcarbamate) (S13-9).
514) Wirkstoffe, die neben einer herbiziden Wirkung gegen Schadpflanzen auch Safenerwirkung an Kulturpflanzen wie Reis aufweisen, wie z. B. "Dimepiperate" oder "MY-93" (S-1 -Methyl-1 -phenylethyl-piperidin-1 - carbothioat), das als Safener für Reis gegen Schäden des Herbizids Molinate bekannt ist,514) active substances which, in addition to a herbicidal activity against harmful plants, also have safener action on crops such as rice, such as, for example, rice. "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate), which is known as a safener for rice against damage by the herbicide Molinate,
"Daimuron" oder "SK 23" (1-(1 -Methyl-1 -phenylethyl)-3-p-tolyl-harnstoff), das als Safener für Reis gegen Schäden des Herbizids Imazosulfuron bekannt ist, "Cumyluron" = "JC-940" (3-(2-Chlorphenylmethyl)-1 -(1 -methyl-1 -phenyl- ethyl)harnstoff, siehe JP-A-60087254), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "Methoxyphenon" oder "NK 049" (S.S'-Dimethyl^-methoxy-benzophenon), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "CSB" (1-Brom-4-(chlormethylsulfonyl)benzol) von Kumiai, (CAS-Reg. Nr. 54091-06-4), das als Safener gegen Schäden einiger Herbizide in Reis bekannt ist."Daimuron" or "SK 23" (1- (1-methyl-1-phenylethyl) -3-p-tolyl-urea) known as safener for rice against damage of the herbicide imazosulfuron, "cumyluron" = "JC-" 940 "(3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, see JP-A-60087254) known as safener for rice against damage of some herbicides, "Methoxyphenone" or "NK 049"(S.S'-dimethyl ^ -methoxy-benzophenone), which is known as safener for rice against damage of some herbicides, "COD" (1-bromo-4- (chloromethylsulfonyl) benzene) of Kumiai, (CAS Reg. No. 54091-06-4), which is known as safener against damage of some herbicides in rice.
S15) Wirkstoffe, die vorrangig als Herbizide eingesetzt werden, jedoch auchS15) active substances, which are primarily used as herbicides, but also
Safenerwirkung auf Kulturpflanzen aufweisen, z.B.Safeners on crops, e.g.
(2,4-Dichlorphenoxy)essigsäure (2,4-D), (4-Chlorphenoxy)essigsäure,(2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid,
(R,S)-2-(4-Chlor-o-tolyloxy)propionsäure (Mecoprop),(R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),
4-(2,4-Dichlorphenoxy)buttersäure (2,4-DB),4- (2,4-dichlorophenoxy) butyric acid (2,4-DB),
(4-Chlor-o-tolyloxy)essigsäure (MCPA),(4-chloro-o-tolyloxy) acetic acid (MCPA),
4-(4-Chlor-o-tolyloxy)buttersäure, 4-(4-Chlorphenoxy)buttersäure,4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid,
3,6-Dichlor-2-methoxybenzoesäure (Dicamba),3,6-dichloro-2-methoxybenzoic acid (Dicamba),
1-(Ethoxycarbonyl)ethyl-3,6-dichlor-2-methoxybenzoat (Lactidichlor-ethyl).1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).
Einige der Safener sind auch als Herbizide bekannt und entfalten somit neben der Herbizidwirkung bei Schadpflanzen zugleich auch Schutzwirkung bei den Kulturpflanzen.Some of the safeners are also known as herbicides and thus, in addition to the herbicidal action in harmful plants, at the same time also have a protective effect on the crop plants.
Die Gewichtsverhältnisse von Herbizid(mischung) zu Safener hängt im Allgemeinen von der Aufwandmenge an Herbizid und der Wirksamkeit des jeweiligen Safeners ab und kann innerhalb weiter Grenzen variieren, beispielsweise im Bereich von 200:1 bis 1 :200, vorzugsweise 100:1 bis 1 :100, insbesondere 20:1 bis 1 :20. Die Safener können analog den erfindungsgemäßen Verbindungen oder deren Mischungen mit weiteren Pestiziden formuliert werden und als Fertigformulierung oder Tankmischung mit den erfindungsgemäßen Verbindungen bereitgestellt und angewendet werden.The weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20. The safeners can be formulated analogously to the compounds according to the invention or mixtures thereof with further pesticides and can be provided and used as finished formulation or tank mixture with the compounds according to the invention.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher weise verdünnt z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.For use are present in commercial form formulations optionally diluted in the usual way z. As in wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der erfindungsgemäßen Verbindungen. Sie kann innerhalb weiter Grenzen schwanken, z. B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 5 kg/ha.With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of the invention. It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha.
BeispieleExamples
A. SynthesebeispieleA. Synthesis Examples
Nachfolgend sind Synthesen erfindungsgemäßer Verbindungen beispielhaft beschrieben, ohne dass diese Beispiele limitierenden Charakter haben.Syntheses of compounds according to the invention are described below by way of example, without these examples having a limiting character.
1. (6-Amino-5-chlor-2-(2,6-dichlorphenyl)pyrimidin-4-yl)propandinitril (Bsp. Nr. 174) Stufe A:1. (6-Amino-5-chloro-2- (2,6-dichlorophenyl) pyrimidin-4-yl) propanedinitrile (Ex. No. 174) Step A:
Zu einer Lösung von 72 mg Malondinitril in 10 ml THF wird bei 00C Natriumhydrid (45 mg als 60%ige Suspension in Mineralöl) zugegeben und die Mischung anschließend für 30 Minuten bei Raumtemperatur gerührt. 4,5,6-Trichlor-2-(2,6-dichlorphenyl)pyrimidin (0,30 g; analog folgender Vorschrift hergestellt: K. Findeisen, K. Wagner, Synthesis 1978, 40-42) wird zugegeben und die Reaktionsmischung bei Raumtemperatur über Nacht gerührt. Der Ansatz wird auf 10 ml gesättigte Ammoniumchlorid-Lösung gegeben, mehrmals mit Ethylacetat extrahiert und die vereinigten organischen Phasen mit gesättigter Natriumchlorid-Lösung gewaschen. Nach dem Trocknen über Magnesiumsulfat wird das Lösungsmittel im Vakuum eingeengt, wodurch Verbindung Nr. 534 erhalten wird. Stufe B:To a solution of 72 mg of malononitrile in 10 ml of THF at 0 0 C sodium hydride (45 mg as a 60% suspension in mineral oil) was added and the mixture then stirred for 30 minutes at room temperature. 4,5,6-Trichloro-2- (2,6-dichlorophenyl) pyrimidine (0.30 g, prepared analogously to the following procedure: K. Findeisen, K. Wagner, Synthesis 1978, 40-42) is added and the reaction mixture at Room temperature stirred overnight. The mixture is added to 10 ml of saturated ammonium chloride solution, extracted several times with ethyl acetate and the combined organic phases are washed with saturated sodium chloride solution. After drying over magnesium sulfate, the solvent is concentrated in vacuo to give compound no. 534. Level B:
Das erhaltene Produkt wird in 5 ml konzentrierter Ammoniaklösung suspendiert und 8 Stunden lang bei 1500C im geschlossenen Gefäß in einem Mikrowellengerät zur Reaktion gebracht. Die Lösung wird anschließend imThe resulting product is suspended in 5 ml of concentrated ammonia solution and reacted for 8 hours at 150 ° C. in a closed vessel in a microwave oven. The solution is then in the
Vakuum auf das halbe Volumen eingeengt und mit 2N Salzsäure angesäuert. Der ausgefallene Feststoff wird mit Wasser und Ethylacetat gewaschen und anschließend getrocknet. Es werden 0,19 g (61 % der Theorie) des gewünschten Produkts erhalten.Vacuum to half the volume and acidified with 2N hydrochloric acid. The precipitated solid is washed with water and ethyl acetate and then dried. There are obtained 0.19 g (61% of theory) of the desired product.
2. [6-Amino-5-chlor-2-phenylpyrimidin-4-yl]propandinitril (Bsp. Nr. 1 )2. [6-Amino-5-chloro-2-phenylpyrimidin-4-yl] propanedinitrile (Ex. No. 1)
Die Substanz wird analog der Vorschrift zu Bsp. Nr. 174 dargestellt. Die Ausgangssubstanz, 4,5,6-Trichlor-2-phenylpyrimidin erhält man nach literaturbekannter Methode: K. Findeisen, K. Wagner, Synthesis 1978, 40-42.The substance is prepared analogously to the procedure for Ex. No. 174. The starting material, 4,5,6-trichloro-2-phenylpyrimidine is obtained by literature methods: K. Findeisen, K. Wagner, Synthesis 1978, 40-42.
3. [6-Amino-5-chlor-2-(4-chloφhenyl)pyrimidin-4-yl]propandinitril (Bsp. Nr. 29) Die Substanz wird analog der Vorschrift zu Bsp. Nr. 174 dargestellt. Die Ausgangssubstanz, 4,5,6-Trichlor-2-(4-chlorphenyl)pyrimidin erhält man nach literaturbekannter Methode: K. Findeisen, K. Wagner, Synthesis 1978, 40-42.3. [6-Amino-5-chloro-2- (4-chlorophenyl) pyrimidin-4-yl] propanedinitrile (Ex. No. 29) The substance is prepared analogously to the procedure for Ex. No. 174. The starting substance, 4,5,6-trichloro-2- (4-chlorophenyl) pyrimidine is obtained by literature methods: K. Findeisen, K. Wagner, Synthesis 1978, 40-42.
4. [5-Chlor-2-(4-chlorphenyl)-6-(methylamino)pyrimidin-4-yl]propandinitril (Bsp. Nr. 41 )4. [5-Chloro-2- (4-chlorophenyl) -6- (methylamino) pyrimidin-4-yl] propanedinitrile (Ex. 41)
Die Substanz erhält man analog der Vorschrift zu Bsp. Nr. 174. In der Stufe B wird jedoch Methylamin (40% Lösung in MeOH) eingesetzt und die Reaktion bei 1200C für eine Stunde im Mikrowellengerät durchgeführt.The substance is obtained analogously to the procedure for Ex. No. 174. However, in step B, methylamine (40% solution in MeOH) is used and the reaction is carried out at 120 0 C for one hour in a microwave oven.
5. [6-Amino-5-chlor-2-(3-fluorphenyl)pyrimidin-4-yl]propandinitril (Bsp. Nr. 80) Die Substanz wird analog der Vorschrift zu Bsp. Nr. 174 dargestellt. Die Ausgangssubstanz, 4,5,6-Trichlor-2-(3-fluorphenyl)pyrimidin erhält man analog der literaturbekannten Methode: K. Findeisen, K. Wagner, Synthesis 1978, 40-42. 6. (6-Amino-5-chlor-2-methylpyrimidin-4-yl)propandinitril (Bsp. Nr. 272) Die Substanz wird analog der Vorschrift zu Bsp. Nr. 174 dargestellt. Die Ausgangssubstanz, 4,5,6-Trichlor-2-methylpyrimidin erhält man nach iiteraturbekannter Methode: H. Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961 , 26, 1874-1877.5. [6-Amino-5-chloro-2- (3-fluorophenyl) pyrimidin-4-yl] propanedinitrile (Ex. No. 80) The substance is prepared analogously to the procedure for Ex. No. 174. The starting material, 4,5,6-trichloro-2- (3-fluorophenyl) pyrimidine is obtained analogously to the method known from the literature: K. Findeisen, K. Wagner, Synthesis 1978, 40-42. 6. (6-Amino-5-chloro-2-methylpyrimidin-4-yl) propanedinitrile (Ex. No. 272) The substance is prepared analogously to the procedure for Ex. No. 174. The starting substance, 4,5,6-trichloro-2-methylpyrimidine is obtained by the method known in the literature: H. Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961, 26, 1874-1877.
7. (6-Amino-5-chlor-2-tert-butylpyrimidin-4-yl)propandinitril (Bsp. Nr. 277) Die Substanz wird analog der Vorschrift zu Bsp. Nr. 174 dargestellt. Die Ausgangssubstanz, 4,5,6-Trichlor-2-tert-butylpyrimidin erhält man in Analogie zur literaturbekannten Methode: H. Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961 , 26, 1874-1877.7. (6-Amino-5-chloro-2-tert-butylpyrimidin-4-yl) propanedinitrile (Ex. No. 277) The substance is prepared analogously to the procedure for Ex. No. 174. The starting material, 4,5,6-trichloro-2-tert-butylpyrimidine is obtained in analogy to the method known from the literature: H. Gershon, K. Dittmer, R. Braun, J. Org. Chem. 1961, 26, 1874-1877.
8. Ammonium-[6-amino-5-chlor-2-(2,6-dichlorphenyl)pyrimidin-4-yl](dicyan)methanid (Bsp. Nr. 371 ) Es werden 100 mg der Verbindung Bsp. Nr. 174 in Ammoniaklösung (2M in EtOH, 2ml) vollständig gelöst, im Vakuum bei 400C eingeengt und der erhaltene Feststoff getrocknet. Es werden 104 mg des gewünschten Produkts erhalten.8. Ammonium [6-amino-5-chloro-2- (2,6-dichlorophenyl) pyrimidin-4-yl] (dicyano) methanide (Ex. No. 371) There are added 100 mg of Compound Ex. No. 174 in ammonia solution (2M in EtOH, 2ml) completely dissolved, concentrated in vacuo at 40 0 C and the resulting solid was dried. There are obtained 104 mg of the desired product.
9. Ammonium-[6-amino-5-chlor-2-phenylpyrimidin-4-yl](dicyan)methanid (Bsp. Nr. 288)9. Ammonium [6-amino-5-chloro-2-phenylpyrimidin-4-yl] (dicyan) methanide (Ex. No. 288)
Die Substanz wird analog der Vorschrift zu Bsp. Nr. 371 dargestellt.The substance is prepared analogously to the procedure for Ex. No. 371.
10. Natrium-lβ-amino-δ-chlor^^-chlorphenyO-pyrimidin^-y^dicyanJmethanid (Bsp. Nr. 304) Durch Zugabe einer stöchiometrischen Menge von Natriummethylat zur in Ethanol gelösten Verbindung Bsp. Nr. 29 kann das entsprechende Natriumsalz nach dem Einengen im Vakuum und anschließendem Trocknen erhalten werden.10. Sodium lβ-amino-δ-chloro ^^ - chlorophenyl-pyrimidine ^ -dicyanomethanide (Ex. No. 304) By adding a stoichiometric amount of sodium methylate to the compound Compound No. Ex. 29 dissolved in ethanol, the corresponding sodium salt are obtained after concentration in vacuo and subsequent drying.
11. Ammonium-Iβ-amino-δ-chlor^^-chlorphenylJ-pyrimidin^-y^dicyanJmethanid (Bsp. Nr. 308)11. Ammonium-1β-amino-δ-chloro ^^ - chlorophenyl-1-pyrimidine-cyano-dicyanomethane (Ex. No. 308)
Die Substanz wird analog der Vorschrift zu Bsp. Nr. 371 dargestellt. 12. Ammonium-[6-amino-5-chlor-2-(3-fluoφhenyl)-pyrimidin-4-yl](dicyan)methanid (Bsp. Nr. 332) Die Substanz wird analog der Vorschrift zu Bsp. Nr. 371 dargestellt.The substance is prepared analogously to the procedure for Ex. No. 371. 12. Ammonium [6-amino-5-chloro-2- (3-fluorophenyl) -pyrimidin-4-yl] (dicyan) methanide (Ex. 332) The substance is prepared analogously to the procedure for Ex. No. 371 shown.
Die in den nachfolgenden Tabellen 1 - 4 beschriebenen Verbindungen (Nr. 1 - 463) erhält man analog zu den oben beschriebenen Synthesebeispielen. Die in Tabelle 5 beschriebenen Verbindungen (Nr. 464 - 585) erhält man analog zu Synthesebeispiel A1 , Stufe A.The compounds (Nos. 1 to 463) described in Tables 1 to 4 below are obtained analogously to the synthesis examples described above. The compounds (Nos. 464-585) described in Table 5 are obtained analogously to Synthesis Example A1, Step A.
In den Tabellen 1-5 bedeuten:In Tables 1-5, mean:
Me = MethylMe = methyl
Et = Ethyl cBu = Cyclobutyl cPr = Cyclopropyl iPr = Isopropyl cHex = Cyclohexyl tBu = tert-ButylEt = ethyl cBu = cyclobutyl cPr = cyclopropyl iPr = isopropyl cHex = cyclohexyl tBu = tert-butyl
Ph = PhenylPh = phenyl
Vin = VinylVin = vinyl
Ac = AcetylAc = acetyl
HaI = Halogen Hal = halogen
Tabelle 1 : Verbindungen der Formel (I) Table 1: Compounds of the formula (I)
Tabelle 2: Verbindungen der Formel (I) Table 2: Compounds of the formula (I)
Tabelle 3: Salze der Verbindungen der Formel (I) Table 3: Salts of the compounds of the formula (I)
Tabelle 4: Salze der Verbindungen der Formel (I) Table 4: Salts of the compounds of the formula (I)
Physikalische Daten ausgewählter Verbindungen der Tabellen 1 -4: Physical data of selected compounds of Tables 1 -4:
Methode ^.: 11H-NMR (Bruker DRX-400, 400 MHz1 294K, DMSO-d6l TMS = 0.0 ppm)Method ^ .: 1 1 H-NMR (Bruker DRX-400, 400 MHz 1 294K, DMSO-d 6l TMS = 0.0 ppm)
Tabelle 5: Verbindungen der Formel (II)Table 5: Compounds of the formula (II)
ll ) ll)
Physikalische Daten ausgewählter Verbindungen der Tabelle 5: Physical Data of Selected Compounds of Table 5:
Bsp. Nr. DatenEx. No. of data
472. 8.43 (d, 2H), 8.35 (d, 2H)472. 8.43 (d, 2H), 8.35 (d, 2H)
478. 8.25 (m, 2H), 7.30 (m, 2H)478. 8.25 (m, 2H), 7.30 (m, 2H)
480. 8.21 (d, 2H), 7.54 (d, 2H)480. 8.21 (d, 2H), 7.54 (d, 2H)
492. 8.19 - 8.14 (m, 2H), 7.59 - 7.48 (m, 2H)492. 8.19 - 8.14 (m, 2H), 7.59 - 7.48 (m, 2H)
494. 8.16 (m, 2H), 7.53 (m, 2H)494. 8.16 (m, 2H), 7.53 (m, 2H)
510. 7.51 (m, 1 H), 7.41 (m, 1 H), 7.33 (m, 1 H)510. 7.51 (m, 1H), 7.41 (m, 1H), 7.33 (m, 1H)
534. 7.58 - 7.53 (d, 2H), 7.50 - 7.45 (m, 1 H)534. 7.58 - 7.53 (d, 2H), 7.50 - 7.45 (m, 1H)
542. 7.68 (m, 2H), 7.50 (d, 1 H)542. 7.68 (m, 2H), 7.50 (d, 1 H)
576. 2.28 (s, 3H)576. 2.28 (s, 3H)
586. 7.67 (d, 1 H), 7.07 (m, 2H), 2.50 (s, 3H), 2.30 (s, 3H)586. 7.67 (d, 1H), 7.07 (m, 2H), 2.50 (s, 3H), 2.30 (s, 3H)
587. 7.98 (m, 1 H), 7.29 (m, 1 H), 7.19 (m, 1 H)587. 7.98 (m, 1H), 7.29 (m, 1H), 7.19 (m, 1H)
588. 8.33 (d, 2H), 8.05 (d, 2H), 4.35 (q, 2H), 1.33 (t, 3H)588. 8.33 (d, 2H), 8.05 (d, 2H), 4.35 (q, 2H), 1.33 (t, 3H)
589. 7.80 (m, 1 H), 7.09 (m, 2H), 2.35 (s, 3H)589. 7.80 (m, 1H), 7.09 (m, 2H), 2.35 (s, 3H)
590. 7.94 (dd, 1 H), 7.83 (dd, 1 H), 7.38 (m, 1 H), 2.29 (s, 3H)590. 7.94 (dd, 1H), 7.83 (dd, 1H), 7.38 (m, 1H), 2.29 (s, 3H)
591. 8.08 (m, 2H), 7.22 (m, 1 H), 2.28 (s, 3H)591. 8.08 (m, 2H), 7.22 (m, 1H), 2.28 (s, 3H)
Methode *.: 11H-NMR (Bruker DRX-400, 400 MHz, 294K, DMSO-d6) TMS = 0.0 ppm)Method * .: 1 1 H-NMR (Bruker DRX-400, 400 MHz, 294K, DMSO-d 6) TMS = 0.0 ppm)
B. FormulierungsbeispieleB. Formulation Examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile einer erfindungsgemäßen Verbindung und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dust is obtained by mixing 10 parts by weight of a compound according to the invention and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile einer erfindungsgemäßen Verbindung, 64 Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt. c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew.-Teile einer erfindungsgemäßen Verbindung mit 6 Gew.-Teilen Alkylphenolpolyglykolether (©Triton X 207), 3 Gew.-Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischemb) A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of a compound according to the invention, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyltaurine sodium as wetting and dispersing agent, and grinded in a pin mill. c) A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound according to the invention with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71% by weight. Divide paraffinic
Mineralöl (Siedebereich z.B. ca. 255 bis über 277 0C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.Mineral oil (boiling range, for example, about 255 to about 277 0 C) mixed and ground in a ball mill to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen einer erfindungsgemäßen Verbindung, 75 Gew.-Teilen Cyclohexanon alsd) An emulsifiable concentrate is obtained from 15 parts by weight of a compound according to the invention, 75 parts by weight of cyclohexanone as
Lösungsmittel und 10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.Solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
e) Ein in Wasser dispergierbares Granulat wird erhalten indem man 75 Gew.-Teile einer erfindungsgemäßen Verbindung, 10 Gew.-Teile ligninsulfonsaures Calcium,e) A water-dispersible granule is obtained by reacting 75 parts by weight of a compound according to the invention, 10 parts by weight of calcium lignosulfonate,
5 Gew.-Teile Natriumlaurylsulfat,5 parts by weight of sodium lauryl sulfate,
3 Gew.-Teile Polyvinylalkohol und3 parts by weight of polyvinyl alcohol and
7 Gew.-Teile Kaolin mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser als Granulierflüssigkeit granuliert.7 parts by weight of kaolin mixed, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 25 Gew.-Teile einer erfindungsgemäßen Verbindungf) A water-dispersible granules are also obtained by adding 25 parts by weight of a compound of the invention
5 Gew.-Teile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium 2 Gew.-Teile oleoylmethyltaurinsaures Natrium,5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium 2 parts by weight of oleoylmethyltaurinate sodium,
1 Gew.-Teil Polyvinylalkohol,1 part by weight of polyvinyl alcohol,
17 Gew.-Teile Calciumcarbonat und17 parts by weight of calcium carbonate and
50 Gew.-Teile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet. C. Biologische Beispiele50 parts by weight of water are homogenized on a colloid mill and pre-comminuted, then ground on a bead mill and the resulting suspension is sprayed in a spray tower by means of a single-fluid nozzle and dried. C. Biological examples
Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im NachauflaufHerbicidal action or crop plant compatibility postemergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden inSeeds of monocotyledonous or dicotyledonous weeds are cultivated in
Holzfasertöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. 2 bis 3 Wochen nach der Aussaat werden die Versuchspflanzen im Einblattstadium behandelt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wässrigeWood fiber pots laid in sandy loam soil, covered with soil and grown in the greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage. The compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then treated as aqueous
Suspension bzw. Emulsion mit einer Wasseraufwand menge von umgerechnet 600 bis 800 l/ha unter Zusatz von 0,2 Gew.-% Netzmittel auf die grünen Pflanzenteile gesprüht. Nach ca. 3 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen wird die Wirkung der Präparate visuell im Vergleich zu unbehandelten Kontrollen bonitiert (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen).Suspension or emulsion sprayed with an amount of water equivalent of 600 to 800 l / ha with the addition of 0.2 wt .-% wetting agent on the green parts of plants. After about 3 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal activity in percent (%): 100% effect = plants are dead, 0% effect = like control plants).
Wie die Ergebnisse in Tabelle 7 zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Nachauflaufwirksamkeit gegen ein breites Spektrum von Ungräsem und Unkräutern auf. Beispielsweise hat die Verbindung Nr. 1 und andere Verbindungen aus den Tabellen 1 bis 4 sehr gute herbizide Wirkung von mindestens 80 % gegen Schadpflanzen wie Matricaria inodora, Polygonum (Fallopia) convolvulus und Veronica persica im Nachauflaufverfahren bei einer Aufwandmenge von 0.32 kg und weniger Aktivsubstanz pro Hektar. Gleichzeitig lassen erfindungsgemäße Verbindungen Gramineen-Kulturen wie Gerste, Weizen, Roggen, Hirse, Mais oder Reis im Nachauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt. Einige Substanzen schonen darüber hinaus auch zweikeimblättrige Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben oder Kartoffeln. Die erfindungsgemäßen Verbindungen zeigen teilweise eine hohe Selektivität und eignen sich deshalb im Nachauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Kulturen. Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im VorauflaufAs the results in Table 7 show, compounds of the invention have good post-emergence herbicidal activity against a broad spectrum of weeds and weeds. For example, the compound No. 1 and other compounds from Tables 1 to 4 have very good herbicidal activity of at least 80% against harmful plants such as Matricaria inodora, Polygonum (Fallopia) convolvulus and Veronica persica postemergence at an application rate of 0.32 kg and less active substance per hectares. At the same time, compounds according to the invention leave gramineous crops such as barley, wheat, rye, millet, corn or rice undamaged after the postemergence process, even at high doses of active ingredient. In addition, some substances also protect dicotyledonous crops such as soya, cotton, rapeseed, sugar beet or potatoes. Some of the compounds according to the invention show a high selectivity and are therefore suitable postemergence for combating undesired plant growth in agricultural crops. Herbicidal action or crop plant compatibility in the pre-emergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Holzfasertöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wässrige Suspension bzw. Emulsion in einer Aufwandmenge entsprechend 320 g / Hektar mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha unter Zusatz von 0,2% Netzmittel auf die Oberfläche der Abdeckerde appliziert.Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in sandy loam in wood fiber pots and covered with soil. The compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then treated as aqueous suspension or emulsion at a rate of application corresponding to 320 g / ha with a water application rate of 600 to 800 l / ha with addition of 0, 2% wetting agent applied to the surface of the cover soil.
Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Testpflanzen gehalten. Die visuelle Bonitur der Schäden an den Versuchspflanzen erfolgt nach einer Versuchszeit von 3 Wochen im Vergleich zu unbehandelten Kontrollen (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen).After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. The visual assessment of the damage to the test plants is carried out after a test period of 3 weeks in comparison to untreated controls (herbicidal action in percent (%): 100% effect = plants are dead, 0% effect = like control plants).
Wie die Ergebnisse in Tabelle 6 zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und Unkräutern auf. Beispielsweise haben die Verbindungen Nr. 9 und andere Verbindungen aus den Tabelle 1 bis 4 sehr gute herbizide Wirkung gegen Schadpflanzen wie Sinapis alba, Avena fatua, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus und Alopecurus myosuroides im Vorauflaufverfahren bei einer Aufwandmenge von 0,32 kg Aktivsubstanz pro Hektar. Gleichzeitig lassen erfindungsgemäße Verbindungen zweikeimblättrige Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben oder Kartoffeln im Vorauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt. Einige Substanzen schonen darüber hinaus auch Gramineen-Kulturen wie Gerste, Weizen, Roggen, Hirse, Mais oder Reis. Die erfindungsgemäßen Verbindungen zeigen teilweise eine hohe Selektivität und eignen sich deshalb im Vorauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Kulturen. Tabelle 6: Biologische Wirkung im VorauflaufAs shown in the results in Table 6, compounds of the present invention have good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds. For example, compounds Nos. 9 and other compounds shown in Tables 1 to 4 have very good herbicidal activity against harmful plants such as Sinapis alba, Avena fatua, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus and Alopecurus myosuroides preemergence at an application rate of 0.32 kg of active ingredient per hectare. At the same time, compounds according to the invention leave undigested dicotyledonous crops such as soybean, cotton, oilseed rape, sugar beets or potatoes in pre-emergence even at high doses of active ingredient. Some substances also protect graminaceous crops such as barley, wheat, rye, millet, corn or rice. Some of the compounds according to the invention show a high selectivity and are therefore suitable in the pre-emergence process for controlling undesired plant growth in agricultural crops. Table 6: Biological effects in pre-emergence
OO O OO O
OOOO
Abkürzungen: 00 N3Abbreviations: 00 N3
ABUTH Abutilon theophrastiABUTH Abutilon theophrasti
ALOMY Alopecurus myosuroidesALOMY Alopecurus myosuroides
AMARE Amaranthus retroflexusAMARE Amaranthus retroflexus
LOLMU Lolium multiflorumLOLMU Lolium multiflorum
MATIN Tripleurospermum inodorumMATIN triple urospermum inodorum
PHBPU Ipomoea purpureaPHBPU Ipomoea purpurea
POLCO Polygonum convolvulusPOLCO Polygonum convolvulus
10 SETVI Setaria viridis10 SETVI Setaria viridis
VERPE Veronica persicaVERPE Veronica persica
VIOTR Viola tricolor VIOTR viola tricolor
Tabelle 7: Biologische Wirkung im NachauflaufTable 7: Biological effects in postemergence
OO CO OO CO
OOOO
OO cnOO cn
Abkürzungen: siehe Tabelle 6, darüber hinaus: ECHCG Echinochloa crus-galli OO STEME Stellaria media Abbreviations: see Table 6, in addition: ECHCG Echinochloa crus-galli OO STEME Stellaria media

Claims

Patentansprüche claims
1. Verbindung der Formel (I) und deren N-Oxide und agrochemisch geeignete1. Compound of formula (I) and their N-oxides and agrochemically suitable
Salze,salts
worin die Reste folgende Bedeutung aufweisen:wherein the radicals have the following meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (Ci-CβJAlkyl, (d- C6)Haloalkyl, (CrC4)Hydroxyalkyl, (C2-C4)Alkoxyalkyl, (C2-C4)Haloalkoxyalkyl, (C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C2-C4)Alkinyl, (C3-C4)Haloalkinyl, Hydroxy, (CrC4)AIkOXy, (d-C4)Haloalkoxy, (C2-C4)Alkenyloxy, (C2-C4)Haloalkenyloxy, (C2-C4)Alkinyloxy, (C3-C4)Haloalkinyloxy, (CrC4)Alkylthio, (CrC4)Haloalkylthio,R 1 is phenyl, optionally substituted by 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 -alkyl, (C 1 -C 6 ) -haloalkyl, (C 1 -C 4 ) -hydroxyalkyl, (C 2 -) C 4 ) alkoxyalkyl, (C 2 -C 4 ) haloalkoxyalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl, (C 2 -C 4 ) alkynyl, (C 3 -C 4 ) haloalkynyl, hydroxy, (CrC 4) -alkoxy, (dC 4) haloalkoxy, (C 2 -C 4) alkenyloxy, (C 2 -C 4) haloalkenyloxy, (C 2 -C 4) alkynyloxy, (C 3 -C 4) Haloalkinyloxy, (CrC 4 ) alkylthio, (C r C 4 ) haloalkylthio,
(C1-C4)AIkYlSuIfJrIyI, (CrC4)Haloalkylsulfinyl, (CrC4)Alkylsulfonyl, (Cr C4)Haloalkylsulfonyl, (C2-C4)Alkenylthio, (C2-C4)Haloalkenylthio, (C2- C4)Alkenylsulfinyl, (C2-C4)Haloalkenylsulfinyl, (C2-C4)Alkenylsulfonyl, (C2- C4)Haloalkenylsulfonyl, (C2-C4)Alkinylthio, (C3-C4)Haloalkinylthio, (C3- C4)Alkinylsulfinyl, (C3-C4)Haloalkinylsulfinyl, (C3-C4)Alkinylsulfonyl, (C3-(C 1 -C 4) AIkYlSuIfJrIyI, (C r C4) haloalkylsulfinyl, (C r C 4) alkylsulfonyl, (C r C4) haloalkylsulfonyl, (C 2 -C 4) alkenylthio, (C 2 -C 4) Haloalkenylthio , (C 2 - C 4) alkenylsulfinyl, (C 2 -C 4) Haloalkenylsulfinyl, (C 2 -C 4) alkenylsulphonyl, (C 2 - C 4) Haloalkenylsulfonyl, (C 2 -C 4) alkynylthio, (C 3 - C 4) Haloalkinylthio, (C 3 - C 4) alkynylsulfinyl, (C 3 -C 4) Haloalkinylsulfinyl, (C 3 -C 4) alkynylsulfonyl, (C 3 -
C4)Haloalkinylsulfonyl, (d-CβJAlkylamino, (C2-C8)Dialkylamino, (C2- CβJAlkylcarbonyl, (C2-C6)Alkoxycarbonyl, (C2-C6)Alkylaminocarbonyl, (C3- C8)Dialkylaminocarbonyl, (C3-C6)Trialkylsilyl, Phenyl, Phenoxy oder einen 5- oder 6-gliedrigen heteroaromatischen Ring, jeder Phenyl-Ring, Phenoxy-Ring oder 5-oder 6-gliedrige heteroaromatische Ring optional substituiert mit 1-3C 4) Haloalkinylsulfonyl, (d-CβJAlkylamino, (C 2 -C 8) dialkylamino, (C 2 - CβJAlkylcarbonyl, (C 2 -C 6) alkoxycarbonyl, (C 2 -C 6) alkylaminocarbonyl, (C 3 - C 8) Dialkylaminocarbonyl, (C 3 -C 6 ) trialkylsilyl, phenyl, phenoxy or a 5- or 6-membered heteroaromatic ring, each phenyl ring, phenoxy ring or 5- or 6-membered heteroaromatic ring optionally substituted with 1-3
Substituenten unabhängig voneinander ausgewählt aus R28; oder zwei benachbarte Reste Rx bilden gemeinsam eine Gruppe -OCH2O-, -CH2CH2O-, -OCH2CH2O-, -OCH(CH3)O-, -OC(CH3)2O-, -OCF2O-, -CF2CF2O-, -OCF2CF2O- oder -CH=CH-CH=CH-; oder (CrCβJ-Alkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander Halogen, (C2-C6)Alkenyl, (C2-C6)Haloalkenyl, (d-C3)Alkoxy, (d- C2)HaIOaIkOXy, (C-ι-C3)Alkylthio, (Ci-C2)Haloalkylthio oder gegebenenfalls substituiertes Aryl bedeuten; oderSubstituents independently selected from R 28 ; or two adjacent radicals R x together form a group -OCH 2 O-, -CH 2 CH 2 O-, -OCH 2 CH 2 O-, -OCH (CH 3 ) O-, -OC (CH 3 ) 2 O- , -OCF 2 O-, -CF 2 CF 2 O-, -OCF 2 CF 2 O- or -CH = CH-CH = CH-; or (C 1 -C 6 ) -alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) Haloalkyl, (C 1 -C 3) alkylthio, (C 1 -C 2 ) haloalkylthio or optionally substituted aryl;
(C2-C6)-Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander Halogen, (CrC6)Alkyl, (CrC6)Haloalkyl, (CrC3)Alkoxy, (Cr C2)Haloalkoxy, (d-C3)Alkylthio oder (d-C2)Haloalkylthio bedeuten;(C 2 -C 6) alkenyl optionally substituted by 1-3 radicals R z, which are independently halogen, (CrC 6) alkyl, (CrC 6) haloalkyl, (CrC 3) alkoxy, (C r C 2) haloalkoxy , (dC 3 ) alkylthio or (dC 2 ) haloalkylthio;
R2 ist H, F, Cl, Br, I, CN, NO2, OR5, SR6 oder N(R7)R8; worin R5 H, (CrC4)Alkyl oder (CrC3)Haloalkyl ist, R6 H, (CrC4)Alkyl oder (CrC3)Haloalkyl ist und R7 und R8 unabhängig voneinander H oder (Ci-C4)Alkyl sind;R 2 is H, F, Cl, Br, I, CN, NO 2 , OR 5 , SR 6 or N (R 7 ) R 8 ; wherein R 5 is H, (CrC 4 ) alkyl or (C r C 3 ) haloalkyl, R 6 is H, (C r C 4 ) alkyl or (C r C 3 ) haloalkyl and R 7 and R 8 are independently H or (C 1 -C 4 ) alkyl;
R3 ist H, (CrC4)Alkyl optional substituiert mit 1-2 Resten R9, (C2-C4)Alkenyl optional substituiert mit 1-2 Resten R10, oder (C2-C4)Alkinyl optional substituiert mit 1-2 Resten R11; oder R3 ist C(=O)R12, NO2, OR13, S(O)2R14, N(R15)R16 oder N=C(R17)R18;R 3 is H, (C r C 4 ) alkyl optionally substituted with 1-2 radicals R 9 , (C 2 -C 4 ) alkenyl optionally substituted with 1-2 radicals R 10 , or (C 2 -C 4 ) alkynyl optionally substituted with 1-2 radicals R 11 ; or R 3 is C (= O) R 12 , NO 2 , OR 13 , S (O) 2 R 14 , N (R 15 ) R 16 or N = C (R 17 ) R 18 ;
R4 ist H, (CrC4)Alkyl optional substituiert mit 1-2 Resten R9, oder C(=O)R12; oder R3 und R4 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- oder -(CH2)2O(CH2)2-, jede Gruppe optional substituiert mit 1-2 Resten R19; oderR 4 is H, (C r C 4 ) alkyl optionally substituted with 1-2 radicals R 9 , or C (= O) R 12 ; or R 3 and R 4 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, -CH 2 CH = CHCH 2 - or - (CH 2 ) 2 O (CH 2 ) 2 -, each Group optionally substituted with 1-2 radicals R 19 ; or
R3 und R4 bilden gemeinsam eine Gruppe =C(R20)N(R21)R22 oder =C(R23)OR24;R 3 and R 4 together form a group = C (R 20 ) N (R 21 ) R 22 or = C (R 23 ) OR 24 ;
dabei ist jeder Rest R9, R10 und R11 unabhängig voneinander Halogen, (Creach radical R 9 , R 10 and R 11 is independently halogen, (Cr
C3)AIkOXy, (CrC3)Haloalkoxy, (CrC3)Alkylthio, (CrC3)Haloalkylthio, Amino, (CrC3)Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl;C 3 ) alkoxy, (C r C 3 ) haloalkoxy, (C r C 3 ) alkylthio, (C r C 3 ) haloalkylthio, amino, (CrC 3 ) alkylamino, (C 2 -C 4 ) dialkylamino or (C 2 - C 4 ) alkoxycarbonyl;
R12 ist jeweils unabhängig voneinander H, (Ci-C4)Alkyl, (CrC3)Haloalkyl, (Cr C4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy;R 12 is each independently H, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy or benzyloxy;
R13 ist H, (CrC4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26;R 13 is H, (C r C 4 ) alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O) OR 26 ;
R14 ist (d-C4)Alkyl oder (CrC3)Haloalkyl; R15 ist H, (C1-C4)AIkVl oder C(=O)R27;R 14 is (dC 4 ) alkyl or (C r C 3 ) haloalkyl; R 15 is H, (C 1 -C 4 ) Al kVl or C (= O) R 27 ;
R16 ist H oder (d-C4)Alkyl;R 16 is H or (dC 4 ) alkyl;
R17 ist H, (Ci-C4)Alkyl oder Phenyl optional substituiert mit 1-3 Resten, welche voneinander unabhängig CH3, Cl oder OCH3 bedeuten; R18 ist H oder (CrC4)Alkyl; oder R17 und R18 bilden gemeinsam eine GruppeR 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals which independently CH 3 , Cl or OCH 3 ; R 18 is H or (C 1 -C 4 ) alkyl; or R 17 and R 18 together form a group
-(CH2)4- oder -(CH2)S-;- (CH 2 ) 4 - or - (CH 2 ) S-;
R19 ist jeweils unabhängig voneinander Halogen, (CrC3)Alkyl, (CrC3)Alkoxy, (CrC3)Haloalkoxy, (d-C3)Alkylthio, (CrC3)Haloalkylthio, Amino, (C1-R 19 is each independently halogen, (CrC 3) alkyl, (CrC 3) alkoxy, (CrC 3) haloalkoxy, (dC 3) alkylthio, (CrC 3) haloalkylthio, amino, (C 1 -
C3)Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl; R20 ist H oder (CrC4)Alkyl; R21 und R22 sind unabhängig voneinander H oder (CrC4)Alkyl; oder R21 und R22 bilden gemeinsam eine Gruppe -(CH2J4-, -(CH2)5-, -CH2CH=CHCH2- oder -(CH2)2O(CH2)2-;C 3 ) alkylamino, (C 2 -C 4 ) dialkylamino or (C 2 -C 4 ) alkoxycarbonyl; R 20 is H or (C r C 4 ) alkyl; R 21 and R 22 are independently H or (C 1 -C 4 ) alkyl; or R 21 and R 22 together form a group - (CH 2 J 4 -, - (CH 2 ) 5 -, -CH 2 CH = CHCH 2 - or - (CH 2 ) 2 O (CH 2 ) 2 -;
R23 ist H oder (Ci-C4)Alkyl;R 23 is H or (C 1 -C 4 ) alkyl;
R24 ist (CrC4)Alkyl;R 24 is (C r C 4 ) alkyl;
R25 ist H, (CrC4)Alkyl, (d-C3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oderR 25 is H, (CrC 4) alkyl, (dC 3) haloalkyl, (C r C 4) alkoxy, phenyl, phenoxy or
Benzyloxy; R26 ist H, (d-C4)Alkyl oder (CrC4)Alkoxy; R27 ist H, (C1-C4) Alkyl oder Benzyl; und R28 ist jeweils unabhängig voneinander Halogen, Cyano, Nitro, (C-i-CβJAlkyl, (C1-benzyloxy; R 26 is H, (dC 4) alkyl or (C r C 4) alkoxy; R 27 is H, (C 1 -C 4 ) alkyl or benzyl; and R 28 are each independently halogen, cyano, nitro, (Ci-CβJAlkyl, (C 1 -
C6)Haloalkyl, (C2-C4)AI kenyl, (C2-C4)Haloalkenyl, (C3-C4)Alkinyl, (C3-C 6 ) haloalkyl, (C 2 -C 4 ) alkylene, (C 2 -C 4 ) haloalkenyl, (C 3 -C 4 ) alkynyl, (C 3 -
C4)Haloalkinyl, (C1-C4)AIkOXy, (Ci-C4)Haloalkoxy, (Ci-C4)Alkylthio, (C1- C4)Haloalkylthio, (CrC4)Alkylsulfinyl, (CrC4)Alkylsulfonyl, (CrC4)Alkylamino,C 4) haloalkynyl, (C 1 -C 4) -alkoxy, (Ci-C 4) haloalkoxy, (Ci-C 4) alkylthio, (C 1 - C 4) haloalkylthio, (C r C4) alkylsulfinyl, (C r C 4 ) alkylsulfonyl, (C r C 4 ) alkylamino,
(C2-C8)Dialkylamino, (C2-C4)Alkylcarbonyl, (C2-C6)Alkoxycarbonyl, (C2-(C 2 -C 8 ) dialkylamino, (C 2 -C 4 ) alkylcarbonyl, (C 2 -C 6 ) alkoxycarbonyl, (C 2 -
CβJAlkylaminocarbonyl, (Cs-CsJDialkylaminocarbonyl oder (C3-C6)Trialkylsilyl.Cβ-alkylaminocarbonyl, (Cs-Cs) dialkylaminocarbonyl or (C 3 -C 6 ) trialkylsilyl.
2. Verbindung der Formel (I) und deren N-Oxide und agrochemisch geeignete Salze gemäß Anspruch 1 , worin die Reste folgende Bedeutung aufweisen:2. Compound of formula (I) and their N-oxides and agrochemically suitable salts according to claim 1, wherein the radicals have the following meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (Ci-C6)Alkyl, (C1- C6)Haloalkyl, (C2-C4)Alkoxyalkyl, (C2-C4)Haloalkoxyalkyl, (C2-C4)Alkenyl, (C2- C4)Haloalkenyl, (C2-C4)Alkinyl, (C3-C4)Haloalkinyl, Hydroxy, (CrC4)Alkoxy, (C1-R 1 is phenyl, optionally substituted by 1-3 R x radicals, which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 4 ) alkoxyalkyl, (C 2 -C 4) haloalkoxyalkyl, (C 2 -C 4) alkenyl, (C 2 - C 4) haloalkenyl, (C 2 -C 4) alkynyl, (C 3 -C 4) haloalkynyl, hydroxy, (C r C 4 ) alkoxy, (C 1 -
C4)Haloalkoxy, (CrC4)Alkylthio, (CrC^Haloalkylthio, (CrC4)Alkylsulfinyl, (Cr C4)Alkylsulfonyl, (CrC6)Alkylamino, (C2-C8)Dialkylamino, -OCH2O-, -CH2CH2O-, -OCH2CH2O-, -OCH(CH3)O-, -OC(CH3)2O-, -OCF2O-, -CF2CF2O- oder - OCF2CF2O-, wobei die acht letztgenannten Substituenten jeweils durch zwei benachbarte Rx gebildet werden; oderC 4) haloalkoxy, (C r C4) alkylthio, (CrC ^ haloalkylthio, (C r C4) alkylsulfinyl, (C r C 4) alkylsulfonyl, (C r C6) alkylamino, (C 2 -C 8) dialkylamino , -OCH 2 O-, -CH 2 CH 2 O-, -OCH 2 CH 2 O-, -OCH (CH 3 ) O-, -OC (CH 3 ) 2 O-, -OCF 2 O-, -CF 2 CF 2 O- or -OCF 2 CF 2 O-, wherein the eight latter substituents are each formed by two adjacent R x ; or
(d-CβJAlkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (C2-C6)Alkenyl, (C2-C6)Haloalkenyl, (Cr C3)AIkOXy, (CrC2)Haloalkoxy, (CrC3)Alkylthio, (CrC2)Haloalkylthio oder gegebenenfalls substituiertes Phenyl; oder(C 1 -C 6 -alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) Haloalkoxy, (C r C 3 ) alkylthio, (C r C 2 ) haloalkylthio or optionally substituted phenyl; or
(C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (CrCe)AIkVl1 (CrC6)Haloalkyl, (CrC3)Alkoxy, (C1-C2)HaIOaIkOXy, (d-C3)Alkylthio oder (CrC2)Haloalkylthio;(C 2 -C 6 ) alkenyl, optionally substituted by 1-3 radicals R z , which independently of one another are halogen, (CrCe) Al kVl 1 (CrC 6 ) haloalkyl, (C r C 3 ) alkoxy, (C 1 -C 2 ) Haloalkoxy, (dC 3 ) alkylthio or (C r C 2 ) haloalkylthio;
R2 ist H, F, Cl, Br, I, CN oder NO2;R 2 is H, F, Cl, Br, I, CN or NO 2 ;
R3 ist H, (CrC4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, C(=O)R12, OR13, N(R15JR16 oder N=C(R17)R18; R4 ist H oder (CrC4)Alkyl, optional substituiert mit 1-2 Resten R9, oder C(=O)R12; oder R3 und R4 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)5-, -(CH2)2O(CH2)2- oder =C(R20)N(R21)R22;R 3 is H, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, C (= O) R 12 , OR 13 , N (R 15 JR 16 or N = C (R 17 ) R 18 ; R 4 is H or (C r C 4 ) alkyl, optionally substituted with 1-2 radicals R 9 , or C (= O) R 12 ; or R 3 and R 4 together form a group - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 O (CH 2 ) 2 - or = C (R 20 ) N (R 21 ) R 22 ;
dabei ist jeder Rest R9, R10 und R11 unabhängig voneinander Halogen, (Creach radical R 9 , R 10 and R 11 is independently halogen, (Cr
C3)AIkOXy, (CrC3)Haloalkoxy, (CrC3)Alkylthio, (CrC3)Haloalkylthio, Amino, (d-C3)Alkylamino, (C2-C4)Dialkylamino oder (C2-C4)Alkoxycarbonyl;C 3 ) alkoxy, (CrC 3 ) haloalkoxy, (C r C 3 ) alkylthio, (C r C 3 ) haloalkylthio, amino, (dC 3 ) alkylamino, (C 2 -C 4 ) dialkylamino or (C 2 -C 4 ) alkoxycarbonyl;
R12 ist jeweils unabhängig voneinander H, (CrC4)Alkyl, (d-C3)Haloalkyl, (Cr C4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy;R 12 is each independently H, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy or benzyloxy;
R13 ist H, (CrC4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26;R 13 is H, (C r C 4 ) alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O) OR 26 ;
R15 ist H, (CrC4)Alkyl oder C(=O)R27; R16 ist H oder (CrC4)Alkyl;R 15 is H, (C r C 4 ) alkyl or C (= O) R 27 ; R 16 is H or (C r C 4 ) alkyl;
R17 ist H, (d-C4)Alkyl oder Phenyl optional substituiert mit 1-3 Resten, welche voneinander unabhängig CH3, Cl oder OCH3 bedeuten; R18 ist H oder (Ci-C4)Alkyl; oder R17 und R18 bilden gemeinsam eine GruppeR 17 is H, (C 1 -C 4 ) alkyl or phenyl optionally substituted with 1-3 radicals independently of one another representing CH 3 , Cl or OCH 3 ; R 18 is H or (Ci-C 4) alkyl; or R 17 and R 18 together form a group
-(CHz)4- oder -(CHz)5-; R20 ist H oder (CrC4)Alkyl;- (CHz) 4 - or - (CHz) 5 -; R 20 is H or (C r C 4 ) alkyl;
R21 und R22 sind unabhängig voneinander H oder (CrC4)AIKyI; oder R21 and R22 bilden gemeinsam eine Gruppe -(CH2)4-, -(CH2)S-, -CH2CH=CHCH2- oderR 21 and R 22 are independently H or (CrC 4 ) AIKyI; or R 21 and R 22 together form a group - (CH 2 ) 4 -, - (CH 2 ) S-, -CH 2 CH = CHCH 2 - or
-(CH2)2O(CH2)2-; R25 ist H, (CrC4)Alkyl, (Ci-C3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder- (CH 2 ) 2 O (CH 2 ) 2 -; R 25 is H, (C r C 4 ) alkyl, (Ci-C 3 ) haloalkyl, (C r C 4 ) alkoxy, phenyl, phenoxy or
Benzyloxy; undbenzyloxy; and
R26 ist H, (CrC4)Alkyl oder (C1-C4)AIkOXy.R 26 is H, (C r C 4 ) alkyl or (C 1 -C 4 ) alkoxy.
3. Verbindung der Formel (I) und deren N-Oxide und agrochemisch geeignete Salze gemäß Anspruch 1 oder 2, worin die Reste folgende Bedeutung aufweisen:3. A compound of formula (I) and their N-oxides and agrochemically suitable salts according to claim 1 or 2, wherein the radicals have the following meaning:
R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Carboxyl, Cyano, Nitro, (CrC6)Alkyl, (C1-R 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently of one another are halogen, carboxyl, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -
C6)Haloalkyl, (C1-C4)AIkOXy, (CrC4)Haloalkoxy, (CrC6)Alkylamino, (C2- C8)Dialkylamino,C 6) haloalkyl, (C 1 -C 4) -alkoxy, (C r C4) haloalkoxy, (C r C6) alkylamino, (C 2 - C 8) dialkylamino
-OCH2O-, -OCH2CH2O- oder -OCH(CH3)O-, wobei die drei letztgenannten Substituenten jeweils durch zwei benachbarte Rx gebildet werden; oder (CrCe)AIkVl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (C1-C3)AIkOXy, (CrC2)Haloalkoxy oder unsubstituiertes oder durch ein oder mehrere Halogene substituiertes Phenyl; oder-OCH 2 O-, -OCH 2 CH 2 O- or -OCH (CH 3 ) O-, wherein the last three substituents are each formed by two adjacent R x ; or (CrCe) AlkVl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 1 -C 3 ) alkoxy, (C 1 -C 2 ) haloalkoxy or unsubstituted or substituted by one or more halogens phenyl; or
(C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (CrCβ)Alkyl, (d-CβJHaloalkyl, (C1-C3)AIkOXy oder (CrC2)Haloalkoxy; R2 ist F1 Cl, Br, I oder NO2; R3 ist H, (CrC4)Alkyl, ( C2-C4)AI keny I, C(=O)R12, worin R12 H, (CrC4)Alkyl, (C1-(C 2 -C 6 ) alkenyl, optionally substituted by 1-3 radicals R z , which independently of one another are halogen, (C 1 -C 6) alkyl, (C 1 -C 6 haloalkyl, (C 1 -C 3 ) alkoxy or (C 1 -C 2 ) haloalkoxy; R 2 is F 1 Cl, Br, I or NO 2 ; R 3 is H, (C r C 4 ) alkyl, (C 2 -C 4 ) alkynyl I, C (= O) R 12 , wherein R 12 is H , (C r C 4 ) alkyl, (C 1 -
C3)Haloalkyl, (C1-C4)AIkOXy, Phenyl, Phenoxy oder Benzyloxy ist, oder OR13, worin R13 H, (CrC4)Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26 ist, worin R25 H, (CrC4)Alkyl, (CrC3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy ist, und R26 H, (d-C4)Alkyl oder (CrC4)Alkoxy ist; R4 ist H oder (CrC4)Alkyl; oderC 3) haloalkyl, (C 1 -C 4) -alkoxy, phenyl, phenoxy or benzyloxy, or OR 13 wherein R 13 is H, (C r C4) alkyl, (C r C 3) haloalkyl or CHR 25 C ( O) oR 26 wherein R 25 is H, (CrC 4) alkyl, (CrC 3) haloalkyl, (C r C 4) alkoxy, phenyl, phenoxy or benzyloxy, and R 26 is H, (dC 4) alkyl or ( C r C 4 ) is alkoxy; R 4 is H or (C r C 4 ) alkyl; or
R3 und R4 bilden gemeinsam eine Gruppe -(CH2)2O(CH2)2-.R 3 and R 4 together form a group - (CH 2 ) 2 O (CH 2 ) 2 -.
4. Verbindung der Formel (I) und deren N-Oxide und agrochemisch geeignete Salze gemäß Anspruch 1 oder 2, worin die Reste folgende Bedeutung aufweisen: R1 ist Phenyl, optional substituiert mit 1-3 Resten Rx, welche unabhängig voneinander bedeuten Halogen, Cyano, Nitro, (C-i-CβJAlkyl, (CrC6)Haloalkyl, (Ci-C4)Alkoxy, (CrC4)Haloalkoxy, (Ci-CeJAlkylamino, (C2-C8)Dialkylamino, -OCH2O-, -OCH2CH2O- oder -OCH(CH3)O-; oder4. Compound of formula (I) and their N-oxides and agrochemically suitable salts according to claim 1 or 2, wherein the radicals have the following meaning: R 1 is phenyl, optionally substituted with 1-3 radicals R x , which independently represent halogen , Cyano, nitro, (Ci-CβJAlkyl, (CrC 6 ) haloalkyl, (Ci-C 4 ) alkoxy, (C r C 4 ) haloalkoxy, (Ci-CeJAlkylamino, (C 2 -C 8 ) dialkylamino, -OCH 2 O. -, -OCH 2 CH 2 O- or -OCH (CH 3 ) O-; or
(CrC6)Alkyl, optional substituiert mit 1-3 Resten Ry, welche unabhängig voneinander bedeuten Halogen, (CrC3)Alkoxy oder (CrC2)Haloalkoxy; oder (C2-C6)Alkenyl, optional substituiert mit 1-3 Resten Rz, welche unabhängig voneinander bedeuten Halogen, (CrC6)Alkyl, (CrC6)Haloalkyl, (Ci-C3)AIkOXy oder (CrC2)Haloalkoxy;(C 1 -C 6 ) alkyl, optionally substituted by 1-3 radicals R y , which independently of one another are halogen, (C 1 -C 3 ) alkoxy or (C 1 -C 2 ) haloalkoxy; or (C 2 -C 6) alkenyl optionally substituted by 1-3 radicals R z, which are independently halogen, (CrC 6) alkyl, (CrC 6) haloalkyl, (Ci-C 3) -alkoxy or (C r C 2 ) haloalkoxy;
R2 ist F, Cl, Br oder I;R 2 is F, Cl, Br or I;
R3 ist H, (C1-C4)AIk^, (C2-C4)Alkenyl, C(=O)R12, worin R12 H, (CrC4)Alkyl, (C1- C3)Haloalkyl, (C1-C4)AIkOXy, Phenyl, Phenoxy oder Benzyloxy ist, oder OR13, worin R13 H, (CrC^Alkyl, (CrC3)Haloalkyl oder CHR25C(O)OR26 ist, worin R25 H, (CrC4)Alkyl, (d-C3)Haloalkyl, (CrC4)Alkoxy, Phenyl, Phenoxy oder Benzyloxy ist, und R26 H, (CrC4)Alkyl oder (C1-C4)AIkOXy ist; R4 ist H oder (CrC4)Alkyl; oder R3 und R4 bilden gemeinsam eine Gruppe -(CH2)2O(CH2)2--R 3 is H, (C 1 -C 4 ) Al k, (C 2 -C 4 ) alkenyl, C (= O) R 12 , wherein R 12 is H, (C r C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy or benzyloxy, or OR 13 , wherein R 13 is H, (C 1 -C 4 alkyl, (C r C 3 ) haloalkyl or CHR 25 C (O) OR 26 wherein R 25 is H, (C r C4) alkyl, (dC 3) haloalkyl, (C r C 4) alkoxy, phenyl, phenoxy or benzyloxy, and R (26 H, (C r C4) alkyl or C 1 -C 4) -alkoxy; R 4 is H or (C r C 4) alkyl; or R 3 and R 4 together form a group - (CH 2) 2 O (CH2) 2--
5. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) oder deren N-Oxide und agrochemisch geeignete Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, und b) im Pflanzenschutz übliche Hilfsund Zusatzstoffe.5. An agrochemical composition comprising a) at least one compound of formula (I) or their N-oxides and agrochemically suitable salts, as defined in one or more of claims 1 to 4, and b) auxiliaries and additives customary in crop protection.
6. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) oder deren N-Oxide und agrochemisch geeignete Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, b) einen oder mehrere von Komponente a) verschiedene agrochemische Wirkstoffe, und optional c) im Pflanzenschutz übliche Hilfs- und Zusatzstoffe.6. An agrochemical composition comprising a) at least one compound of the formula (I) or their N-oxides and agrochemically suitable salts as defined in one or more of claims 1 to 4, b) one or more of component a) various agrochemical active ingredients, and optionally c) auxiliaries and additives customary in crop protection.
7. Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur 5 Wachstumsregulierung von Pflanzen, wobei eine wirksame Menge mindestens einer Verbindung der Formel (I) oder deren N-Oxide und agrochemisch geeignete Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, auf die Pflanzen, das Saatgut oder die Fläche, auf der die Pflanzen wachsen, appliziert wird. 0A method for controlling undesirable plants or for regulating the growth of plants, comprising an effective amount of at least one compound of formula (I) or their N-oxides and agrochemically suitable salts as defined in one or more of claims 1 to 4 the plants, the seeds or the area on which the plants grow are applied. 0
8. Verwendung von Verbindungen der Formel (I) oder deren N-Oxide und agrochemisch geeignete Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, als Herbizide oder Pflanzenwachstumsregulatoren.8. Use of compounds of formula (I) or their N-oxides and agrochemically suitable salts as defined in one or more of claims 1 to 4, as herbicides or plant growth regulators.
9. Verwendung nach Anspruch 8, wobei die Verbindungen der Formel (I) oder5 deren N-Oxide und agrochemisch geeignete Salze zur Bekämpfung von9. Use according to claim 8, wherein the compounds of formula (I) or5 their N-oxides and agrochemically suitable salts for controlling
Schadpflanzen oder zur Wachstumsregulierung in Pflanzenkulturen eingesetzt werden.Harmful plants or for growth regulation in crops.
10. Verwendung nach Anspruch 9, wobei die Kulturpflanzen transgene oder nicht0 transgene Kulturpflanzen sind.Use according to claim 9, wherein the crop plants are transgenic or non-transgenic crop plants.
11. Verfahren zur Herstellung einer Verbindung der Formel (I) oder deren N- Oxide und agrochemisch geeignete Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, wobei man 5 a) eine Halogenverbindung der Formel (II)11. A process for the preparation of a compound of the formula (I) or its N-oxides and agrochemically suitable salts as defined in one or more of claims 1 to 4, wherein 5 a) a halogen compound of the formula (II)
mit einem Amin der Formel (IM) HNR3R4 umsetzt, wobei HaI ein Halogenatom ist, die Reste R1, R2 in Formel (II) und R3, R4 in Formel (III) wie in Formel (I) in einem oder mehreren der Ansprüche 1 bis 4 definiert sind, und b) gegebenenfalls die in Schritt a) enthaltene Verbindung der Formel (I) nach üblichen Methoden in ein N-Oxid oder ein agrochemisch geeignetes Salz überführt.with an amine of the formula (IM) HNR 3 R 4 , wherein Hal is a halogen atom is, the radicals R 1 , R 2 in formula (II) and R 3 , R 4 are defined in formula (III) as in formula (I) in one or more of claims 1 to 4, and b) optionally in step a) contained compound of formula (I) by customary methods in an N-oxide or an agrochemically suitable salt.
12. Verbindung der Formel (II), worin die Reste R1 und R2 wie in Formel (I) in einem oder mehreren der Ansprüche 1 bis 4 definiert sind. 12. A compound of the formula (II) in which the radicals R 1 and R 2 are as defined in formula (I) in one or more of claims 1 to 4.
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